Tsegai Tewelde will make his Great Britain debut in the half-marathon Team Cup at the European Athletics Championships in Amsterdam in July.
The Glasgow-based Eritrean, who claimed asylum in 2008, secured an Olympic marathon place after coming 12th in April's London Marathon.
He will be joined in the Netherlands and Rio by Scottish brothers Callum and Derek Hawkins.
Dewi Griffiths, Scott Overall and Jonathan Hay make up the men's team.
Sonia Samuels will run the marathon in Brazil but is skipping the European event to focus on her Olympic preparation.
However, Rio-bound Ally Dixon is in the women's team, along with Tina Muir, Charlotte Purdue, Gemma Steel, Susan Partridge and Lily Partridge.
Neil Black, British Athletics performance director, said: "These are two very strong teams and we firmly believe both can finish on the podium in Amsterdam.
"With a firm focus towards Rio, we have liaised with athletes selected for the Olympics, and their coaches, before making a decision on selection.
"As will be the case with selection for all track disciplines at the European Championships, we believe, for some athletes, running in Amsterdam will benefit their performance in Rio, whilst for others, as in Sonia's case, this competition was never part of the season plan."