Mr Toole, the Member for Bathurst, was elected by a wide margin during Wednesday's Nationals party room meeting to replace John Barilaro, who resigned on Monday.

Nationals MLC and Minister for Mental Health, Regional Youth and Women, Bronnie Taylor, was elected as the party's first female deputy leader.

Wagga-based Nationals MLC Wes Fang said Mr Toole's efforts to upgrade the Snowy Mountains Highway and Gocup Road intersection after a horrific crash showed that the region would benefit from his leadership.

"He brings a wealth of experience. He does it in a different way to Barra [Mr Barilaro] who was very dynamic in an emotional and heart-on-the-sleeve type of way," Mr Fang said.

"I would say that Paul was more reserved, clinical and very technical in the way that he approaches the job, but we know that the two of them were very good at getting outcomes in their different ways."

Mr Fang said Ms Taylor was "the nicest, most kindest and empathetic person in the Parliament ... but she is fierce and the Liberal Party knows it".

Wagga MP Joe McGirr said he had contacted the new Nationals leaders to congratulate them.

"I have worked with both of them on behalf of the electorate; Paul Toole has visited a number of times," Dr McGirr said.

"We have had the Gocup Road issue, we have had the railway culvert issue at Lockhart and he has also launched the transport plan.

"It was very impressive how we was able to swing into action on the Gocup Road issue."

Riverina MP and former federal Nationals leader Michael McCormack congratulated the NSW party's new leaders and said they "will do a wonderful job advocating for regional and rural NSW".

NSW Premier Dominic Perrottet, who was himself voted in as Liberal leader on Tuesday, said Mr Toole was "a fighter and a pragmatist who has a strong track-record of delivering for regional and rural NSW".

"I have worked closely together for many years with Paul, and I know he will bring a steady hand to our efforts to get NSW safely back open and on the path to recovery," Mr Perrottet said.

"Bronnie Taylor has been a powerhouse and worked tirelessly as Minister for Mental Health at a critical time, ensuring vital support is there for people in the aftermath of drought, bushfires and the pandemic."