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The 38-year-old spent 15 seasons with Kent but was released at the end of last season after losing his place to Sam Billings.
He takes over as captain from Australian opener Michael Klinger, who is returning to Gloucestershire for a third year but won’t arrive until June.
Jones, who will play as a specialist batsman, has already played first-class cricket for Gloucestershire after he had a brief loan spell there last season.
He played in three LV= County Championship and two NatWest T20 Blast matches before his stay ended due to an eye infection.
Jones, who has scored 8,615 first-class runs at an average of 32.5 with 15 centuries and 46 fifties, said: “Firstly I’d like to thank Kent County Cricket Club for the fantastic 15 seasons I spent with them.
“I learnt a huge amount there and without the opportunities they gave me I never would have had the career that I have.
“Following an enjoyable month on loan with Gloucestershire during 2014 I am excited to be joining the club on a full-time basis and for the challenges that lie ahead.
“They have a great set-up here and I am looking forward to taking on the role as four-day captain and to working in tandem with Michael Klinger.
“This is a young and talented squad and I relish the opportunity of working with them and to playing a part in their future development.
“I also look forward to working with John Bracewell and his coaching team. They impressed me greatly during my loan period so the chance to work full-time with them I know will have big benefits.”