Viewers of 'Connect the world' will be encouraged to log-on to Skype Chat on CNN.com to discuss the programme after the show.
The sponsorship will be supported by a TV campaign, which will promote Skype business features, such as video calling and cheap international rates.
Ads will appear across Europe, the Middle East, Africa, Asia Pacific and Latin America.
Max Raven, senior vice-president of ad sales at CNN International, said: "This is an ambitious strategic solution that establishes a meaningful brand association for Skype around a core part of CNN's new prime time evening line-up.
"Skype's brand attributes are a great match for our own. We look forward to seeing this commercial partnership executed across CNN's multiplatform distribution internationally, in front of an increasingly engaged audience".
Last week the telephone company's parent eBay announced it was selling a 65 per cent stake in Skype to a group of investors.