Twitter is deep in the throes of a love affair with TV advertising, launching a program to let marketers tweet ads to TV viewers and inking ad deals with 16 media partners, including A+E Networks, Discovery Communications and Major League Baseball.

Social site’s TV ad-targeting service, developed from its acquisition of research firm Bluefin Labs, is designed to deliver promoted tweets to users who have (most likely) been exposed to their ads on TV. Bluefin’s tracking service analyzes when and where ads have run on TV, then identifies users on Twitter who tweeted about the program where the ad aired – and theoretically saw the ads, too.

“Synchronized Twitter and TV ad campaigns make brand messages more engaging, interactive and measurable, while making it easy for marketers to run always-on Twitter campaigns that complement and amplify their TV creative,” Michael Fleischman, Twitter product manager for revenue, wrote in a blog post announcing the service.

Twitter’s TV ad targeting is currently available in beta for U.S. customers that have previously run national TV ad campaigns on the social site.

Meanwhile, Twitter bulked up roster of partners for ad-enabled promotional tweets, which the company now calls “Twitter Amplify.” Those deals augment previous pacts with ESPN, Turner Sports and the NBA, Fox, BBC America, Fuse TV, The Weather Channel.

The new partners are: A&E, theAudience, Bloomberg TV, Clear Channel, Conde Nast, Discovery, MLB,  National CineMedia, New York Magazine, PGA Tour, Penske Media, Time Inc., Vevo, Warner Music, WWE, and Vice. (Disclosure: Penske Media is the owner of Variety.)

Twitter is reportedly also in talks with NBCUniversal and Viacom about similar pacts.

In 2012, 32 million people in the U.S. tweeted about TV programming, according to Twitter. Biggest drivers were major events like the Super Bowl, which drew 24 million tweets, and primetime TV shows like Fox’s “American Idol,” which had 5.8 million tweets during 2012.

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