Currently, only EE has packages, with Zen expected to follow shortly. Often it can take anything from a few months to 1-2 years before a lot of ISPs catch up, which is partly down to the extra work and cost required to support faster tiers.
In terms of Sky, in the past they were often early adopters, but for the FTTP generation they've tended to be laggards. I'd thus expect TalkTalk and Vodafone to launch on the new tiers before Sky does, but you never know.
One catch with TalkTalk is that they're a bit cash strapped, which can make adapting a network to cope with even faster speeds a bit more of a challenge (the may be tempted to push it back).