The twice-weekly service will operate on Wednesday and Friday after launching on December 20.
A third flight is expected to be launched in 2018 and prices will lead in at £651.
The route is expected to be popular with both business and leisure travellers and is the third Brazilian destination for the airline after Salvador de Bahia and Sao Paulo.
To improve connectivity within Brazil, Air Europa maintains a code-sharing agreement with Avianca Brasil, with a codeshare on several weekly domestic flights, which links Recife to other parts of the country.
Air Europa’s UK managing director Colin Stewart said: “We are thrilled about the launch of this route – particularly as Air Europa will be the first airline to fly from London to Recife via Madrid.”