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Petrov, who is now in remission, will work as an assistant to Villa's development coach, Gordon Cowans.
"I'm very excited by this new challenge and I wish to thank the club and the manager, Paul Lambert, for giving me the opportunity to continue my association with Villa, which I have always regarded as a privilege," Petrov told the Villa website.
"I will study for my coaching badges over the coming months and I am looking forward very much to working with Gordon Cowans, someone I know and respect; a true Villa legend."
He added: "The main thing for me, however, is that it is not for sentimental reasons that I will be taking up this role, but because I have something to contribute and I really want to do this.
"The manager allowed me to sit on the bench on Sunday at Wigan so that I could get some perspective from the coaching and management side.
"I travelled with the team and was able to see close-hand and from a new viewpoint just how the first team prepares for a game and the many elements during a game. I'm looking forward to imparting some of my knowledge and continuing to learn as I grow into the role."
Petrov, 33, announced his retirement from football earlier this month, having initially been diagnosed with leukaemia in March 2012.
Villa's fans have shown their support for the Bulgarian midfielder, who joined the club from Celtic in 2006, by applauding during the 19th minute of their matches, in reference to his squad number.
