The flight from Heathrow to the Mexican capital will run between June and September 2016.
The service will be operated by one of the airline’s 787 Dreamliner’s.
Chief revenue officer, Anko van der Werff, said: “Aeromexico celebrates its fourth anniversary serving the London-Mexico City route this year, and the addition of this sixth flight confirms its importance for Aeromexico and for both countries, as it has contributed to increasing business, tourist, and cultural exchanges between these two capital cities.”