Not breaking the record but I just learned about this one so I’ll revive this zombie.
Gary Lockwood and Stefanie Powers were married in 1966 and divorced in 1972. Both are still alive so that’s a fifty-four year ongoing ex-marriage.
And a belated correction. Woody Allen and Harlene Rosen were married in 1956. They got divorced in 1962. So Ray Anthony and Mamie Van Doren regain the number one spot.