Former BHP executives John Prescott and Lance Hockridge have won senior QRN positions.
Prescott was previously the chairman of Queensland Rail while Hockridge was chief executive.
There are five new appointees to QRN who were not previously on the board of QR.
The fresh blood includes former Wesfarmers executive director Gene Tilbrook, former Shell chairman Russell Caplan and former Australia Post chairman Graeme John.
Andrea Staines, who was previously an Australian Rail Track Corporation board director and CEO of Australian Airlines, will also join the QRN board along with Sydney-based lawyer John Atkin.
QR board member Allan Davies, who was once a director of rival Pacific National, will also join the QRN board.
"It's a huge vote of confidence in the future of QR National that this group of respected business leaders have been prepared to bring their excellent reputations and strong track record of success to support and advise the company in its planned transition to a top ASX-listed company," Premier Anna Bligh said.
The coal freight business section of QR will be separated from the passenger business on July 1 and is expected to be privatised in the December quarter.
Some reports suggest the float of QRN could give the company a market cap of $7 billion.
Meanwhile, an alliance of the 14 largest coal companies in Queensland plans to make its own bid for the coal chain assets.
Headed by former New South Wales premier Nick Greiner, the Queensland Coal Industry Rail Group consists of Anglo American Metallurgical Coal, BHP Billiton, BHP Billiton Mitsubishi Alliance, Ensham Resources, Yancoal Australia, Jellinbah Resources, Macarthur Coal, New Hope, Peabody Energy, QCoal, Rio Tinto Coal Australia, Vale, Wesfarmers Resources and Xstrata Coal.