The deal will allow customers to watch live boxing and wrestling events through Sky Sports Box Office, as well as extending a continuing wholesale deal giving access to the main Sky Sports and Sky Movies channels.
It builds on an agreement earlier this year allowing TalkTalk customers to buy a "day pass" for Sky's sports channels through its internet TV service NOW TV on the YouView platform.
The Box Office service can already be accessed by customers of Virgin Media in the UK and UPC in Ireland.
Sky is battling BT over sport after the telecoms giant encroached on its dominance of Premier League football with a three-year deal to show 38 games a season, before snatching Champions League rights for three years from 2015 for £897 million.
The satellite broadcaster has responded with the launch of a new channel, Sky Sports 5, showcasing Champions League football until then, as well as Spanish and Dutch league games. This will also be available through TalkTalk under today's deal.
Mai Fyfield, group director of strategy and business development for Sky said: "As we continue to increase our investment in high-quality TV, we want to continue to broaden the distribution of our content and grow our content related revenues."
The announcement came as TalkTalk reported trading figures showing it had added 185,000 net new TV customers in the first quarter to June 30, giving a total base of 1.1 million, helping revenue rise 3.1% year-on-year to £434 million.
The company said it also added 10,000 net broadband customers and that it was on track to meet its targets for the full year.
Chief executive Dido Harding said: "Our strategy for growth continues to deliver according to plan, and we are delighted to report another quarter of base growth and year-on-year revenue progress."