Mark Speakman on Saturday announced he would vote 'yes' in the referendum because he believed the potential rewards outweighed the potential risk.
He maintained he would not take an active role in the referendum or advise others how to vote.
Liberals for Yes co-convenor Sean Gordon welcomed Mr Speakman's stance, saying a voice to parliament would lead to better outcomes for Aboriginal and Torres Strait Islander peoples.
"Mark Speakman has shown real leadership by supporting constitutional recognition for Indigenous people and giving them a say on matters that affect them to help close the gap," Mr Gordon said.
Mr Speakman previously made clear he would allow opposition MPs freedom to choose how they vote in the referendum.
The Liberal leader has called for changes to the proposal being put to the Australian people, urging the government to separate proposals for constitutional recognition and a voice to form two different questions.
Indigenous Australians Minister Linda Burney said she was proud there was bipartisan support for the voice in NSW but the referendum question would not be changed.
"The prime minister was very clear at Garma last weekend," she said on Saturday.
"We will be proceeding with the referendum in the way in which it's been requested."
Liberals around the country remain divided on the voice referendum, with WA Liberal leader Libby Mettam this week withdrawing her support for the 'yes' vote.
Victorian Opposition Leader John Pesutto has given coalition MPs the freedom to choose how they vote but is yet to reveal his personal position, as is Queensland Opposition Leader David Crisafulli.
Leader of Australia's sole Liberal government, Tasmanian Premier Jeremy Rockliff, plans to vote 'yes' in the referendum.