VOD is a kind of pay per view service with fees ranging from 0$ (free) to 6.99$ (HD film). You rent a film or a show (whitout commercials) for 24 hours. You may watch it anay number of times during that time period.
You won't find first time viewing of program such as Lost. There is some french sitcom or drama program from the previous weeks, usualy free.
Usualy movies are available a few weeks after they appear in rental store. I think this is a rule enforced by the movies studios distributors to protect the rental store market. They may change those rules but i don't think that they will offer movies before the DVDs unless they want to kill the DVD market.