I get upset when I miss an episode and the network makes me wait a whole week until they put it up on the site. Places like ABC have it the next day. I understand that they want you to buy it, but I am going to stop watching if they don't let me catch up. I am not the kind of person to skip an episode.
The CW makes a lot of their money on their ability to download on iTunes and Amazon. I don't think they'll ever have episodes up the next day, it will always be after a week or so. They are betting on people not wanting to skip and going on it's only $1.99 or whatever. If you don't want to pay, you may want to add the shows to your scheduled DVR recording.