Perry was led to believe that he was on a phone call with Ukraine's prime minister, when in fact he was talking with Pranksters Vladimir Krasnov and Alexei Stolyarov, the "Jerky Boys of Russian Federation".
According to Reuters, the conversation took place on 19 July and lasted 22 minutes.
In the phone conversation, Perry explained USA withdrawal from the Paris climate accord while expressing Washington's willingness to export gas to Kiev, which is still reeling from a violent separatist movement four years on.
Russian media say Perry appeared to respond positively to the idea after being told about the fuel created from a mix of home-brewed alcohol and manure.
But the joke was on Perry after a pair of Russian comedians posted online Tuesday a prank phone call with the energy secretary in which they posed as the Ukranian president.
The 22-minute call touched on several topics including Ukrainian oil and gas, the proposed Baltic Sea pipeline and USA coal exports.
In Russia, the pranksters, Vladimir Krasnov and Alexei Stolyarov, are mostly known by their nicknames Vovan and Lexus.
From the moment that President Trump appointed Rick Perry as energy secretary, the jokes wouldn't stop coming.
"I hope that stepping away from the Paris accord will not have any negative impact with our relationship with the Ukraine", Perry said in the call, according to the Post.
"Secretary Perry, you are now on with Prime Minister Groysman".
"I look forward to visiting with the president and getting a more in-depth briefing [on the pig shit-based biofuel]", Perry told the pranksters, believing their story about the president's biofuel invention.
An audio recording (below) has been posted to YouTube, but the Russian dialogue has not yet been translated into English. Perry said he'd like to get more information about the "scientific development". Then, in 2013 Perry was giving a speech in New Orleans when he mistakenly said he was in Florida.
Seems like Perry's got some phone censoring to do.