Pure monoesters of adipic acid are prepared by a process in which(a) a pentenoate is reacted with carbon monoxide and hydrogen at from 90.degree. to 140.degree. C. and under from 5 to 300 bar in the presence of a carbonyl complex of cobalt or of rhodium, and a 5-formylvalerate is separated off, and(b) the 5-formylvalerate thus obtained is oxidized with molecular oxygen, or with a gas containing this, at from 20.degree. to 100.degree. C. under from 1 to 10 bar.