Concorde landed safely at Birmingham on Monday on the first leg of its week-long tour of Britain.
Concorde touched down smoothly at Birmingham
The return trip from Heathrow is part of a five-day schedule of farewell flights also visiting Cardiff, Edinburgh, Manchester and Belfast.
A second group of passengers boarded the flight back to London which departed at 1600 BST.
On board all the 90-minute champagne flights from Heathrow will be 66 competition winners plus a number of
VIPs and key British Airways customers.
All flights will travel at twice the speed of sound - 1350mph - over the Bay of Biscay.
The final journey from Edinburgh on Friday will carry BA staff and will be one of three consecutive flights to land at Heathrow to mark the end of 27 years of commercial Concorde service.
BA's marketing director, Martin George, said: "This is the very last chance many people will have to see Concorde fly and we are delighted that it is visiting all the capital cities in England, Scotland, Northern Ireland and Wales".
In addition the UK tour schedule, there will be one fare-paying transatlantic passenger flight each day from Monday until Thursday, with the final guest-only service leaving New York's JF Kennedy Airport at 7am local time on Friday.
A fall in passenger numbers and high maintenance costs have been blamed for the decision by BA and Air France to retire Concorde. Air France ceased its supersonic flights last May.