Devi
Ashoka was appointed as Viceroy at Ujjain. While going to Ujjain, he halted at Vidisha and met Devi, beautiful daughter of a merchant. He courted her and brought her to Ujjain where she gave birth to Mahendra and Sanghamitra. When Ashoka usupred the throne, Devi didn't follow him to Patliputra but sent her children with their father.
There is speculation why Devi stayed behind in Vidhisha and one of the opinions is that she didn't want to be ruled by Agramahishi (Chief Queen) at Patliputra and preferred to rule his Harem at Vidisha.
Karuwaki
Karuwaki was second wife and Ashoka and mother of his son , Tivala. Her mention is in Ashoka's Allahabad Pillar Inscription in which it's mentioned all the charities made by her should be in her name.
Karuwaki’s origins are not mentioned in any sources whether literary or archeological. Her being related with Kalinga in any way is a pure myth.
Few scholars associate Karuwaki with Tisyarakshita, Ashoka's last wife and second Chief Queen.
Padmavati
Padmavati was one of the wives of Ashoka and her origins are not known. She was mother of his son Kunala.
Kunala was born the day Ashoka had ended up making 84000 stupas. He was first name Dharmavivardhana but due to his bright eyes resembling a Himalayan bird named Kunala, he was named Kunala. He is said to have eyes like a blue lotus, which might be just a metaphor.
Padmavati can not be Asandhimitra because she was alive when the infamous story of blinding of Kunala happened.
As Kunala was the Crown Prince, Padmavati either was from a very rich noble background or she was his absolutely favourite wife but not noble enough to be raised to the rank of Chief Queen.
Asandhimitra
Asandhimitra was the most favourite and influential wife of Ashoka and he raised her to the rank of Chief Queen just because of her wit, merit and sheer loyalty towards the King.
Asandhimitra is said to have a previous birth connection with Ashoka in which they met Lord Buddha and due to their merit rebirthed as King and Queen.
Due to her merit, Ashoka had become impressed and raised her to the dignity of Chief Queen and it brought jealousy of her co-wives. Ashoka showed them Asandhimitra’s worth when even getting royal seal in a test she refused to become a sovereign. Ashoka through this test showed that he trusted Asandhimitra the most and he had her absolute loyalty.
Asandhimitra had the sole right to give advice to Ashoka and even preach him in philosophy. The privilege of having ear of the King was power enough for her to rule over her co-wives.
Asandhimitra is not mentioned to have any children so it's assumed she either was barren or her children didn't get recognition in history.
Tisyarakshita
Tisyarakshita or Tissarakkha was second Chief Queen of Ashoka. She was made Chief Queen after death of his favourite wife Asandhimitra. She is known to have been highly ambitious.
When she had seen Kunala , she fell in love with his Handsomeness and his eyes attracted her. She asked for love from Kunala but he rejected her calling her a mother and her request a sin. Enraged and feared that Kunala would punish her, she once forged a letter of Ashoka to Kunala (when she got sovereignty for few days as she had saved life of Ashoka from a life threatening disease by finding it would be cured by eating onions. Ashoka as a Buddhist didn't eat onions and she convinced him to eat it as medicines) in which it was written Kunal's eyes should be burnt.
Kunala, who was Viceroy in Taxila was shocked and his ministers refused the order so he out of loyalty burned his eyes. He along with his wife Kanchanmala became a wanderer singing songs of his plight.
When Ashoka heard the songs and realised it was his son, he was grieved and when he got to know Tisyarakshita was the reason, he decided to punish her. Kunala asked for mercy for her but Ashoka eventually burned her alive. In few other versions he forgave her when Kunal's eyes magically returned.
In Parishisth Parvan, Kunala was in Ujjain not Taxila and the queen who blinded him is not mentioned and she did it to make her son heir to the throne and not because Kunala had rejected her.
Ashoka had other wives as well who gave birth to his daughter Charumati, his sons Kustana and Jaluka and others who are not named.