Linen, soaked in chemicals, and tied on with a ribbon.
Gabriele Falloppio — the anatomist the fallopian tubes are named after — described a linen sheath soaked in a chemical solution in a work published in 1564, and claimed to have tested it on 1,100 men, none of whom contracted syphilis. It was tied on with a ribbon. It was intended against disease, not pregnancy.
Earlier versions were made from animal intestine, and examples found at Dudley Castle in England date to around 1640. Rubber only arrives after Goodyear’s vulcanisation process in 1839, and latex — thin enough to be acceptable — not until the 1920s.