Google has grown rich with its AdWords and AdSense programs, matching advertisers with online publishers using its search technology.

But a growing number of startups are looking at alternative ways to match these two groups, offering what they say are more targeted, relevant ads for online publishers and promising them a higher click-through rate and therefore more revenue.

Proximic is one of them. The startup on Wednesday announced that it signed deals with two major e-commerce web sites to help them advertise their product catalogues, bringing Proximic’s advertising repository to 50 million items and positioning it to rapidly grow its network of publishers.

Yahoo Shopping, Shopping.com and several other unnamed e-commerce sites entered into business deals with Proximic, which has offices in Palo Alto, California, and Munich, Germany. Its technology, called “pattern proximity,” reads and matches relevant content according to interconnected patterns on a web page while not relying on keywords, which Google does.

“We don’t look at the individual parts of a page, but look at its complete contents,” said Proximic CEO Philipp Pieper. “Therefore the relevance is higher.”

By wooing large catalogue owners like Shopping.com, Proximic avoids having to make thousands of deals with individual merchants. Instead, Proximic will help deliver ads for the catalogue items—anything from a cook book to an inflatable kayak—and then share revenue generated from those ads with the web publisher and catalogue owner.

The merchant behind those catalogue items, such as Target or Amazon, will pay more now that their goods are being viewed more often, but presumably they’ll be making more sales as well.

One hitch in this grand scheme is that Proximic doesn’t yet have a sizeable network of publishers to deliver these ads, kind of like an indy film producer who doesn’t have a theatre to screen his movie.

But Mr. Pieper said that was all part of the plan. The startup had to first focus on either gathering publishers or gathering advertisers, and it chose the latter.

He said Proximic is in negotiation with several publishers, but he wouldn’t name them. British newspaper The Independent and the London- and New York-based Nature Publishing Group are two of the biggest publishers that have already joined Proximic’s network.

Proximic was founded in 2001 and is financially backed by Munich, Germany–based Wellington Partners and New York-based Holtzbrinck Group.