The show is set on the campus of the fictional Bask University, where the characters try to connect via social networking, instant message and text, but wind up miscommunicating.
The program features YouTube stars Jessica Rose, Kevin Wu, Philip DeFranco, Michael Buckley, Kevin Nalty and others.
Fran Shea, general manager of HBOLabs, said the premium network is looking to test whether Web video creators who have a sizable online audience can pull in strong numbers when they are paired together in a new show.
She emphasized that the show is an experiment and not slated to run on-air on HBO. But if successful, "Hooking Up" may appear on HBO on Demand.
"Everyone is looking at this to see what works," she said.
The first two episodes premiere online Oct. 1 at www.hookingupshow.com and on YouTube, Metacafe and Break.com, with subsequent episodes premiering each week. The entire series is 10 episodes.