Angel Maria Villar has resigned from the UEFA vice-presidency and the organisation's executive committee following his arrest in Spain.
Villar, 67, was arrested last week and remains in custody without bail pending an investigation into alleged corruption.
He was suspended from the Spanish Football Federation (RFEF) presidency for one year by Spain's Higher Council of Sport on Tuesday pending the outcome of the investigation, with Juan Luis Larrea named as an interim replacement a day later.
And Villar, who served as acting UEFA president in the wake of Michel Platini's suspension in October 2015, has now given up his responsibilities with European football's governing body.
"On 26 July, 2017, Mr Angel Maria Villar Llona tendered his resignation as Vice President of UEFA and member of the UEFA Executive Committee with immediate effect," UEFA said in a statement.
"Following his resignation, Mr Villar Llona will no longer have any official functions at our organisation.
"UEFA President Aleksander Ceferin has accepted Mr Villar Llona's letter of resignation and has thanked him for his many years of service to European football.
"In view of the on-going court proceedings in Spain, we have no further comments to make on this matter."
Villar, his son Gorka, RFEF economic vice-president Juan Padron and the general secretary of the Tenerife Football Federation Ramon Hernandez were detained following a police raid on the RFEF offices in Madrid.
Police said the men were arrested on suspicion of improper management, misappropriation of funds, corruption and falsifying documents.