Flores, who held a televised press conference today at the Catholic Chancery, said that during the ordeal he tried to find someone to help the man sort out his immigration problems.
The archbishop said his captor, identified as Nelson Antonio Escolero of El Salvador, agreed to release him as long as he kept his promise of finding him a lawyer.
The archbishop was freed at 7 p.m. Wednesday when Escolero surrendered peacefully to police.
Escolero, 40, wanted documents that would keep him from being deported to El Salvador, Flores said.
"I thanked the Lord that I was able to keep my cool. Somehow I was not afraid of him killing me," Flores said. "I was afraid of him killing other people in the building. I really do feel he needs physical and pyschological assistance.
"I pleaded to him in the name of God, in the name of Jesus and in the name of his family, I ask you not to use that weapon," Flores said.
Flores spent the night at a local San Antonio hospital for observation and was released at about 1:15 p.m. today. He held the press conference at 3 p.m. at the Catholic Chancery, where the hostage drama took place from 10 a.m. to 7 p.m. Wednesday.
Escolero was arrested and has been charged with two counts of aggravated kidnapping, for holding Flores and his secretary Myrtle Sanchez hostage.
Flores said when Escolero first entered his office he said "I have to have your help. If you do not assist me, I'm going to commit suicide, and I'm also going to kill you and the people who work here."
Flores and his secretary said they called several government agencies, including the U.S. Attorney General's Office and the Governor's Office, trying to find help for Escolero.
"We tried our best to help him. In keeping with what I promised, I will try to talk to a few lawyers," Flores said. "I am also not going to hold this against his ... wife and children."
Flores said that Escolero spoke of how is family does not have food to eat, and Flores said he will try to help them.