The showrunner told Entertainment Weekly that Andrew Lincoln's former cop and David Morrissey's vicious dictator will finally clash in the zombie drama's 2013 episodes.
"One of the things I'm excited about is we're on the path for this showdown, and the Governor and Rick have still not seen each other as we went through those first eight episodes," he said.
"And the Governor is certainly a big threat to Rick and can destroy his entire group, and the Governor sees Rick as a threat that can destroy all of his plans by showing that he was not the most powerful force in this world... so both guys now have a vendetta against each other."
Mazzara also appeared to confirm that the new Walking Dead episodes will kill off more regular characters, following fellow exec Greg Nicotero's claims that the series was likely to lose additional cast members.
"There will always be death in The Walking Dead, so I don't think anybody should get comfortable," said Mazzara. "The Governor and Rick are gearing up for war, and without sounding silly, there will be blood."
The Walking Dead's final 2012 episode 'Made to Suffer' introduced comic book favourite Tyreese (Chad Coleman) and Mazzara hinted that fans could expect more characters from Robert Kirkman's comics to make their television debut in the future.
"Tyrese is... a wild card," he teased. "He's an interesting character and his priority is keeping his own group safe. I think viewers will be surprised by the twists and turns in the Tyrese story.
"Our comic book fans will still be excited and delighted to see how the story unfolds and how we tell the story. We do have a lot of new surprising material. There's still a major character [from the comics] to appear in the back half, which is very exciting."
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Watch a promo for The Walking Dead below: