Sam Parrett, the current Bromley and Greenwich College principal, has been chosen to lead the new South East London Colleges Group.
Bexley College will be joining the rest of the colleges which will all merge on August 1.
Ms Parrett said the move will “strengthen vocational education and apprenticeship provision” across South East London, “securing a sustainable future across the board”.
She added: “I am confident that future of vocational education in south-east London is very bright and would like to thank everyone involved for getting us to this point.”
Ms Parrett started in FE as a business development manager for work-based learning at Bracknell and Wokingham College, and then became a vice-principal before heading to the Association of South Eastern Colleges. She was also a vice-principal at Plymouth College.
Her move means that Bexley College principal Danny Ridgeway will be retiring when the merger goes ahead.
Mr Ridgeway said: “After 32 years of working in the FE sector, including the last six years as principal of Bexley College, now is the time for me to retire. I shall miss the students, my colleagues and partners, but I know that I am leaving the college in safe hands.”
Meanwhile, Richard Hollywood is to stand down from his position as principal of Mid Cheshire College.
Mr Hollywood had led Mid Cheshire since February 2013, after joining in 2006 as an assistant principal.
A college spokesperson said: “Richard Hollywood has decided to step down from his position as principal of Mid Cheshire College.
“The governors would like to thank him for his service and dedication to the college over the last 10 years.”
Neighbouring West Cheshire College has also revealed its principal Nigel Davies, plus his former deputy principal Adrian Humphreys, have left their posts.
FE Week previously reported that Mr Davies and Mr Humphreys had both moved on “in order to explore new career and other professional opportunities”.
Helen Nellist, who was already a member of the college’s leadership team, was subsequently appointed acting principal.
King George V College in Southport has also said goodbye to its principal Adele Wills, who had led the college since 2010.
A spokesperson informed FE Week that vice-principal Anne-Marie Francis had taken over as acting principal on June 1.
It has also been announced that the principal of Guernsey College, Saboohi Famili, would be leaving her post at the end of the academic year.
Ms Famili said she had been frustrated by slow progress and delays in decision making at Guernsey which led her to leave. She will join London’s Epping Forest College as principal in September.
Guernsey College said its current vice-principal, Louise Misselke, will be made interim principal until a successor is appointed “in the coming months”.