The Doctor Who wiki offers a pretty comprehensive overview of his married life according to the various TV series and prose books.
To date, he's definitely been married at least four times, excluding his relationship with River Song but only two of those marriages took place prior to "Blink".
In rough chronological order
After Gallifrey was destroyed in the Second War in Heaven, the Eighth
Doctor married Scarlette in order to ceremonially tie himself to the
planet Earth. (PROSE: The Adventuress of Henrietta Street)
The Tenth Doctor romanced and later married Elizabeth I. (TV: The End
of Time, The Day of the Doctor) She later declared him an enemy after
he failed to return as promised. (TV: The Shakespeare Code) This did
not appear to be the Doctor's only marriage, as he remarked to Sally
Sparrow about being "rubbish at weddings, especially my own." (TV:
Blink) In his eleventh incarnation, the Doctor accidentally became
engaged to Marilyn Monroe, and married her the same night in what he
later claimed was not a real chapel. (TV: A Christmas Carol)
It's also worth mentioning that at some point before the events of the First Time War, the Doctor was almost certainly married to an unnamed Galifreyan woman and had several children. He was also then married to another Galifreyan woman (Patience) in his guise as the fifth Doctor.