Australian athlete Shirley Strickland de la Hunty earned the gold medal, setting new World and Olympic records.
Strickland improved upon that with a 10.8 in the semi-final round, joined by Maria Sander and Jean Desforges also running 10.9.
In the final, Blankers-Koen blasted out to a clear early lead over the first hurdle.
At the sixth hurdle, Sander lost her stride and struggled, leaving Maria Golubnichaya in silver position but more than 2 metres behind Strickland.
And those positions held, Strickland well ahead of Golubnichaya, a slowing Sander leaning across the finish line to hold off her teammate Anneliese Seonbuchner for bronze.