The carrier will fly from Palma Mallorca to Heathrow, from March, and to Gatwick from Barcelona next summer.
Palma has not been served from Heathrow since 2009. Vueling will fly daily from Heathrow Terminal 3, where it currently operates daily flights to La Coruna and Bilbao, using an A320.
Vueling will operate a total of nine UK routes next summer.
Edinburgh–Barcelona services will return for the summer season along with four Cardiff routes to Barcelona, Alicante, Palma Mallorca and the new route to Malaga.
Vueling CEO, Alex Cruz, said: “We are delighted to be bolstering our London Heathrow services with this popular route to Palma Mallorca
“This is going to be hugely welcomed by the strong expat community and together with the introduction of London Gatwick–Barcelona flights, also commencing at the end of March, our expanded services from the UK capital form a key part of what will be a fourth consecutive year of growth.”
Palma is an expanding base for Vueling and the airline will be offering 14 direct routes from the airport next summer, including high frequency services from its El Prat Barcelona base.