What an insufferable jerk!
There is not one reason I can think of for Mary Astor to be in love with Robert Ames in this movie. He begins by treating her as some office floozy, patting her and calling her "girlie." Then he uses her knowledge and experience to get ahead but treats her with indifference. He is oblivious to her feelings for him and is disrespectful to her at every turn. So why would she like him even a little bit? He's not very good looking and he certainly doesn't have a great personality.
I just couldn't find it believable. They should have given him some redeemable characteristics if they wanted him to end up with Mary like he did. By that point I just wanted her to run far far away.