The Hollywood star's representative has been forced to remind fans he has "no social media presence" after the arrests of five people were announced this week over the online scam.
Pitt's publicist Matthew Hilktzik told the New York Times newspaper: "It's awful that scammers take advantage of fans' strong connection with celebrities."
He added while he hadn't been aware of the case, fans should note that the actor does not have any authorised social media accounts on the likes of X, Facebook and Instagram, which means fans should never believe anyone posing as him online.
Hilktzik continued: "But this is an important reminder to not respond to unsolicited online outreach, especially from actors who have no social media presence."
In a statement this week by Spain's Interior Ministry, the authorities confirmed three arrests were made last November, and another two in July.
They added that the accused people had allegedly contacted contacted the women on an online fan page for the 'Once Upon A Time In Hollywood' actor while posing as him.
It's said they exchanged messages with the victims, while the statement added that they "managed to make these women believe they had become so close to the well-known American actor that they believed they had a romantic relationship with him".
One woman from Bilbao is said to have sent around ¤150,000 (£125,000) in a series of transfers, while the other, from Granada, sent ¤175,000 (£146,000).
Around ¤85,000 (£71,000) has been recovered amid the investigations, while the unnamed suspects face charges including money laundering and fraud.
Brad is currently promoting his new AppleTV+ series 'Wolfs', and his friend and co-star George Clooney George recently revealed he had pretended to be his pal to prank other celebrities, using stationery purporting to be from the 'Moneyball' star.
He told talk show host Jimmy Kimmel: "I sent [a letter] to Tom Cruise, saying they want to do ['Interview with the Vampire 2'], but this time Brad wants to play Lestat."
And when it came to Meryl Streep, the former 'E.R.' star sent her a gift that 'Brad' felt would come in useful for her.
He explained: "I sent [a letter] to Meryl Streep with a box of CDs for dialect and I said, 'This guy helped me with my accent in Troy and I think it could really help you.' "