Mr Jeyes, aged 53, former general secretary of the Association of Directors of Education in Scotland, has been appointed Cambridgeshire's deputy chief executive with responsibility for children and young people's services.
His unexpected move south comes a few months after Stirling was judged by HMI to be one of Scotland's best-performing authorities, along with South Lanarkshire. Mr Jeyes, who has held the top education post in the authority since council reorganisation in 1995, was praised for his "strong and dynamic" leadership.
Prior to that, he was a divisional assistant director of education with the former Strathclyde Region. His first teaching post, in 1974, was at Smithycroft Secondary in Glasgow.
Corrie McChord, leader of Stirling Council, praised Mr Jeyes for his "consistent commitment to social inclusion". Keith Yates, Stirling's chief executive, was confident he would bring "grist, challenge and humour" to his new post.
Meanwhile, the Scottish Council for Research in Education Centre has appointed a new director. Paul Brna, director of research strategy at Northumbria University's school of informatics, succeeds Valerie Wilson who has retired following the completion of the council's move to the education faculty at Glasgow University.
Dr Brna, who took up his post at the beginning of this month, says his research interests lie in finding ways to improve learning "in a wide range of formal and informal settings with the help of interactive technologies".