Mr. America CAN love the ugly duckling, but it just isn't likely. It is even less likely given that they have never met in person. I believe it is entirely possible to only see a person's personality when you look at them and not their physical shell. I have a long time friend who is physically not all that pretty, but when I see her she is the most beautiful person in the world because of her personality and the kindness of her heart. BUT... most men are very visually based. Especially at first. If this guy had been her friend for years and years and it had turned into something more I would be cheering. But he didn't start focusing on her until she because financially successful.
She needs to guard her heart. Don't let her meet this guy alone. If he really loves her he will come to her and not make her meet him in random, strange places. The men I have known who were in love would have climbed mountains barefoot and nekkid in order to be with the woman they loved. She needs to be very, very careful.