Two 30-second spots, featuring in the February 3 show, will promote C4's Friday night comedy shows My Name is Earl, The IT Crowd and Green Wing.
OMD booked the media in a deal which was done directly with Ricky Gervais' agent. It negotiated the deal based on radio rates.
The deal allows the channel to promote its comedy strand in an otherwise ad-free environment. There is an option to continue the relationship if a second series of Gervais' podcasts is made.
The Ricky Gervais Show is one of podcasting's biggest success stories. Each podcast show gets about 300,000 downloads, according to The Guardian.
The total download figures to date top more than two million. The show is also number one in both the UK and US iTunes charts. OMD's Ian Cairns said: "Running solus advertising in such highly sought after content offers unparalleled cut-through in a fantastically relevant and high-interest environment."
He added: "In the same way Rajar measures listeners, not advertisers, we only quantify the number of people listening.
"It's trying to build awareness."
Cairns believes C4's first podcast advertising appeared as spots on Virgin's podcast of the Pete and Geoff Show early last year.
Rufus Radcliffe, head of marketing for C4, added: "Podcasts are no longer a niche medium and are fast moving into the mainstream.
"We believe advertising in the world's biggest podcast will be an extremely valuable part of our communications plan."
The Ricky Gervais Show deal marks the growing popularity of the podcasting medium as media owners look to deliver their content on multiple platforms.
Earlier this month, Sky unveiled its plans for a weekly current affairs podcast, while The Sun used the medium to run a five-minute interview with the Prime Minister.
Last month, The Daily Telegraph appointed Radio 5 Live presenter Guy Ruddle as the first podcast editor for a British newspaper.