Jones chose Arizona over finalists East Carolina and Oklahoma and received serious interest from several schools, including North Carolina, Auburn, Clemson and Colorado.
His father, former NFL linebacker Robert Jones, confirmed the decision to ESPN.com and said the Wildcats provided the best opportunity to start over his career.
"It's definitely a fresh start," Robert Jones said. "I just think that he felt, 'Hey, I'm going to a new environment. People don't know me, I don't know them and it's a fresh start for me.' I know he wasn't afraid of the challenge. I think just the way things unfolded, it was a better opportunity for him to get maximum opportunities on the field."
The 6-foot-3, 210-pound sophomore wideout is joining a fellow former Longhorn at Arizona, one he became good friends with last year. Redshirt freshman quarterback Connor Brewer announced he was transferring to Arizona on July 30 and is currently practicing with the team.
According to his father, Jones flew to Tucson, Ariz., on Tuesday and is hoping to begin practicing with Arizona on Wednesday. He did not visit Arizona or any other school this summer before reaching his decision.
Jones, an Austin native, appeared in 11 games for the Longhorns as a true freshman and recorded two catches for 25 yards. He was an Under Armour All-American and ESPN 150 recruit coming out of Austin High School, and Jones and Brewer were considered two of the leaders of Texas' No. 3 ranked 2012 recruiting class.
"I think that's a good thing just starting off from a personal side and having a relationship. They built a good relationship before they joined the University of Texas," Robert Jones said. "They've known each other for quite some time. Who knows, it could be Connor throwing to Cayleb in the future. I don't think Connor was the deciding factor, it was more about what's his opportunity and his chances of playing."
The wide receiver announced his intentions to transfer July 25 after serving a suspension that began in March.
Jones had been charged with felony aggravated assault in March for allegedly hitting and breaking the jaw of a Texas tennis player. Those charges were dismissed and reduced to a misdemeanor a month later.
Strong family ties were a major reason why Jones considered ECU. In addition to the chance to play brother Isaiah Jones, a freshman receiver for ECU, it's also their father's alma mater. Robert Jones won three Super Bowls as a linebacker for the Dallas Cowboys and played his college ball for the Pirates.
"East Carolina was in there until the end," Robert Jones said. "I would say that their coaching staff, athletic director, all those guys received Cayleb very well. It would've been good to see them play together, but at same time, my boys are at the age where I want them to choose their own paths and choose a good one. We feel like Arizona is a good choice."
Jones and Brewer will both sit out the 2013 season and have three seasons of eligibility at Arizona.