Solana's decision had been expected but his announcement was the first time he acknowledged it publicly, EUobserver reported Monday.
"I had a 10-year mandate which I have fulfilled," Solana, a former NATO chief and Spanish foreign minister, told a Spanish daily newspaper in an interview. "I do not mean to go any further."
He will become the vice president of the European Commission, chairman of all the European Union foreign minister councils and head of a new EU diplomatic service.
During his time as high representative for common foreign and security policy, Solana established himself as one of the negotiators and speaker for the EU on the Iran nuclear issue.