And Vishnu smilingly spoke to wielder of trident Rudra, 'oh, god the best, whatever element that has emerged from the churning of Milk Ocean by gods, that shall belong to you, isn't it. By virtue of your position as the foremost god among gods, oh, omnicompetent god Shiva, you please accept this poison applying yourself to that position of foremost god, and deeming this poison, haalahala, as a foremost oblation to your godhood'.
Saying so Vishnu, the best one among gods, has disappeared then and there only. And on observing the scare of gods and also on paying heed to the words of the Wielder of Bow called shaar~Nga, namely Vishnu, god Shiva gulped that lethal poison, haalaahala , as if it is ambrosia.
Source : Valmiki Ramayana Bala Kanda Sarga 45
Maharishi Vishwamitra prayed to Mahadeva and obtained all the weapons from him and he also learnt the science of Dhanurveda from Mahadeva.
On going to the mountainsides of Himalayas, whereat it is adored by kinnaraa-s and uragaa-s, the nymphs and nymphean serpents, he that great practiser of ascesis, Vishvamitra, undertook an austere ascesis for the sake of beneficence of the Great God, Shiva.
After a long lost time, Shiva, the God of Gods whose flag bears the sign of Holy Bull, has shown himself to that great-saint Vishvamitra, for He is a ready boon-giver.
'Oh, king, for which purpose you undertook this ascesis that you may tell me. What is it really intended by you and what boon you seek that be made known to me for I am the boon-giver.' Shiva said so to Vishvamitra.
Thus said by God Shiva to Vishvamitra of great ascesis, Vishvamitra on reverencing that Great God Shiva said this way.
Oh! Mahadeva, the Impeccable Great God... providing that you are gladdened by my ascetic devotion, dhanurveda, the Holy Writ of Archery, with its complemental and supplemental Writs, and along with its summational Upanishad-s , together with its preternatural doctrines... they may kindly be bestowed upon me...
' Oh, Exquisite God, whichever missile is there either with gods, or fiends, gandharva-s, yaksha-s, and demons, let it dawn upon me. For you alone are the God of Gods your blessings alone can fulfil my aspiration.' Thus Vishvamitra entreated God Shiva.
So be it!' On sanctifying Vishvamitra and his aspiration thus, the God of Gods, Shiva disappeared.
Source : Valmiki Ramayana Bala Kanda Sarga 55
King Janaka, father of Mata Sita, narrated the story of the bow of Mahadeva.
Oh, godly sage, there was a king renowned as Devaraata, sixth one from Nimi, [the originator of our lineage,] and this bow was handed down to him for custodial care by the Sublime Soul, Shiva...
Once, during the devastation of the Vedic-ritual of Daksha Prajapati, the mettlesome god Rudra, rancorously outstretching the bowstring of this bow, said this to all gods, superciliously..
'Oh, gods, whereby you have not apportioned my portion [of oblations in Vedic-ritual s, as I am also the] desirer of such portion, [thereby] I will shred the highly revered heads of yours with this bow...' [So said Shiva to gods.]
Then, oh, best saint Vishvamitra, all gods are truly dismayed, and on their supplicating, Bhava, namely Shiva, the God of Gods is gladdened...
And that Sublime Soul Shiva gladly gave that bow to all of the great souled gods, and oh, godly saint, then those great souled gods gave this gem of a bow of Shiva, the God of Gods, to our ancestor [Devaraata,] for custodial care...
Source : Valmiki Ramayana Bala Kanda Sarga 66
Bhagwan Parshurama called Mahadeva as the destroyer of Tripura.
Oh, best one among men, out of the two longbows gods gave one to restive Trymbaka, God Shiva for a combat with demon Tripura, and oh, Kakutstha, that bow alone is the annihilator of Tripura, the demon... and you have broken that alone...
Source : Valmiki Ramayana Bala Kanda Sarga 75
Bhagwan Sri Ram had worshipped himself and Mahadeva before entering into the house made by Lakshman ji during their exile.
Having taken bath in the river as prescribed Rama offered oblations to Lord Rudra and Lord Vishnu after offereing tributes to Vaisvadeva. He performed benedictions relating to the purification of house and also a silent prayer as per prescribed rites. He finally offered excellent tributes to the deities, for removing sins.
Source : Valmiki Ramayana Ayodhya Kanda Sarga 56
Mahadeva had come to congratulate Bhagwan Sri Ram after he had killed Ravana and he also informed him about his father Dasaratha.
Hearing the auspicious words thus spoken by Rama, Lord Shiva the Supreme Lord thereupon delivered the following still more beautiful speech:
"O lotus-eyed, long-armed, broad-chested, annihilator of enemies and excellent among those upholding the cause of virtue! Thank heaven! You accomplished this task."
"Fortunately has the fear born of Ravana - which increased the severe darkness on the entire world has been removed by you, on the battle-field, O Rama!"
"You are fit to go to the heaven, by comforting the depressed Bharata and the illustrious Kausalya as well as seeing Kaikeyi and Sumitra, the mother of Lakshmana having got the sovereignty of Ayodhya, bringing delight to your friends, stabilizing the back-bone in the race of Ikshvaku, getting excellent glory by performing a horse-sacrifice and by granting riches to Brahmanas."
Source : Valmiki Ramayana Yuddha Kanda Sarga 119
Bhagwan Sri Ram tells Mata Sita how Mahadeva blessed him and his army before battle.
See this island, located in the middle of the ocean, where my troops were stationed. At this place, the lord Shiva (the supreme deity) formerly bestowed his grace on me
Source : Valmiki Ramayana Yuddha Kanda Sarga 123
JAI SIYA RAM !
HAR HAR MAHADEV !