The couple, both New Jersey natives, had three children, and divorced in 1951, after her husband had a string of extramarital affairs which were made public in Hollywood gossip columns, The New York Times reported.
He married actress and Hollywood bombshell, Ava Gardner, just 10 days after his divorce from Nancy Sinatra.
But the pair remained close until Frank Sinatra's death in 1998 at the age of 82, after a heart attack, the newspaper reported.
The late Nancy Sinatra never remarried and lived a quiet life in Beverly Hills, California and focused on charity work, the newspaper reported.
A spokesperson for the family could not be reached early Saturday, and no other details about her death were available.