Mr Mundine was booed and jeered at by pro-Voice activists as he made his way into an early voting centre in Sydney, shaking hands with people wearing both Yes and No shirts.
The ugly incident was captured by Sky News, showing the vocal opponent of the Voice chatting with locals in a sea of waving signs and chants of “Yes” could be heard.
It comes just hours after Prime Minister Anthony Albanese lashed the No campaign for spreading “misinformation”.
Speaking from Adelaide on Friday morning, Mr Albanese said there was a “certain arrogance that has crept into the No campaign of taking this for granted and taking Australians for granted”.
“Some of the polls forgot to speak with voters,” he said.
Just a day out from the referendum, the polls are not looking good for the Yes camp.
An eleventh hour poll has indicated the Voice will be defeated in a majority of states when they count the referendum votes from 6pm on Saturday, October 14.
But Yes campaigners remain defiant, saying they will fight to the bitter end.
Mr Albanese says he expects Australians to buck the “computer generated polls” and vote in favour of the change.
More to come.