Revealing mistake: When Snow White and Prince Charming hurriedly make their way through the woods in the beginning of the episode, in the shot where Snow White jumps over a log, you can see the face of Ginnifer Goodwin's and Josh Dallas' stunt doubles. Josh Dallas' stunt double can also be seen as Snow and Charming are running thought the woods in the previous shot.
Revealing mistake: After Mr. Gold's group leaves Mary Margaret's apartment, in the wide-shot where Mr. Gold asks Cruella and Maleficent to follow Regina, a direction sign pointing to a shop called "Steveston General Store" can be seen on a building. Steveston is the Canadian town which doubles as the town of Storybrooke on Once Upon a Time. (00:14:30)
Answer: He knows who she is because he knows that the fairy tales are true. He was also shown to sneak out to go see Emma or someone else. Sometimes he succeeded, sometimes he didn't. This is how he knew to look for her despite his strict mother.