Ascaso's was the brother of fellow anarchists Alejandro Ascaso and Domingo Ascaso who all frequently worked together. Alejandro was born on October 17, 1889. Domingo was killed in Barcelona during the 1937 May Riots. He also had a sister named Maria. In 1927 he started a relationship with Berthe Fabert. In 1924 Ascaso settled in Paris and worked in a plumbing factory which aggravated his respiratory problems.