Not exactly. Before signing up for WWE Network this weekend I was trying to find the answer to this question and it wasn’t easy. I browsed through a couple pages of Google result pages and didn’t find an answer to the specific question above so I wanted to answer it here for anyone else wondering the same thing.
If you’re looking to watch episodes of RAW anytime after they air your best bet is still a Hulu Plus subscription. This is because the WWE Network delays episodes of RAW and Smackdown for about three months. For example as of today the most current episode of Smackdown you can watch is the January 23, 2014 episode. As for RAW, the most current episode is the January 19, 2014 episode.
You can, however, watch the most current PPV (which until later tonight is February’s Elimination Chamber), as well as any past PPV and of course any live PPV starting with Wrestlemania XXX tonight.
I hope this clears up any confusion anyone might have. Maybe I just missed the information, but I couldn’t find a clear answer through Google myself.