WWE has added an episode of Saturday Night's Main Event from July 15, 2006 to their On Demand library on the WWE Network. This may mean that the rest of the shows will be up soon. They quietly added an episode of Clash of the Champions days before they released the entire library of shows. You can watch the SNME episode by doing a search for it or go to this link: http://network.wwe.com/video/v33595821
WWE is about to start putting up 1995 episodes of Raw so they're getting close to the Monday Night War episodes. They will be releasing WCW Monday Nitro shows when the Raws on the network get up to September 1995 when Nitro launched.