'Have you ever been on television ?'

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Could be that, could just be that she looks like someone he actually has seen on TV. I like that not everything has a cut and dried explanation.

... sex addicts toads ...
Give up the toad now!

I think that's *exactly* why, mensahcarrelle - Graham asking the television question, plus him quizzing Ann about her marriage indicated to me that he was intensely attracted to her sexually from the very beginning...especially given what happens later: the intimate lunch when he discloses that he's impotent (why on EARTH would you tell a stranger that unless to build intimacy/closeness/safety?), and how he asks Cynthia to let him tape her, but doesn't want to do that with Ann initially...I just had the sense that Graham wanted to be intimate (both physically and emotionally) with Ann early on.

Good question! :)

i think when he first saw her he thinks she's so pretty that she could have been an actress or something, like she's pretty enough to go on tv

I think it's pretty clear that's it, you're given the visual cue beforehand when his camera can clearly be seen in the trunk of his car, this is right before he enters the house and meets Ann and asks her this question.