That entirely depends on which points in their timestreams you ask about. They both travel in time independently of each other. That can mean (& several times has meant) that the Doctor, at a point in his timestream before their wedding, has been with River, at a point in her timestream after their wedding.
To put it mildly, it's complicated even for them, never mind for us. That's why, when they meet, they need to work out where each one of them is in his/her timestream. Time travel means there cannot be a simple, straight answer to a question like this. ("The Husbands of River Song" emphasises this point.)