Irfan Latif has been named as principal of the private school near Westminster Bridge which charges fees of up to £53,000 a year for an A-level course with boarding.
DLD College London – which has students aged 14 to 19 – moved to its new building on the South Bank in 2015.
Mr Latif has joined DLD College London from Sexey's School at Bruton in Somerset where he held the position of headmaster for more than four years.
"I am thrilled to have been appointed the new principal of DLD College London and I am very excited to join this prestigious school which has the students at the heart of its thinking.
"I admire that its roots are borne out of an academic commitment to the community and that student well-being is a central focus.
"By affording opportunities to develop, intellectually, spiritually, emotionally, physically and socially, DLD College London strives to educate the whole person in preparation for an ever-changing and uncertain world.
"My predecessor Rachel Borland has left me with a fine school, which is highly regarded, and I will endeavour to build upon her industry to nurture and strengthen DLD's position as a leading boarding school.
"It is a tremendous honour to lead and serve the DLD community and I will relish taking up the reins of this innovative and forward-thinking school."
DLD College London is part of the Alpha Plus Group which is owned by investment fund DV4, managed by Delancey, whose other assets include a share in the Elephant & Castle Shopping Centre.
DLD's tuition fees for the next academic year range from £19,000 to £29,000 a year. Accommodation in the 250 boarding rooms costs up to £24,000 a year for a 'gold' ensuite room.