Kawhena, also known as Johnny Coffin, was a "national treasure" and was considered one of Goldie's finest works of art, Mr Thomson said.
"People never tire of Goldie."
Another of his paintings, Te Aitu Te Irikau, an Arawa chieftainess, painted in 1911, was expected to bring up to $230,000, he said.
Both oil paintings were being offered for the first time.
Te Aitu Te Irikau was the first of several Goldie painted of the Arawa chieftainess. It was in an original Goldie frame and has been in a private collection in Hawke's Bay since the 1930s.
"The two Goldies are exceptional examples of Goldie's ability to show the detail of Maori culture in the moko and weaving," Mr Thomson said.
"He also captures the soul of his subjects. The mood he portrays in the eyes of Kawhena is quite compelling and with Te Aitu Te Irikau, it is very easy to imagine her as a woman of great reverence and mana but also as a person with a very close understanding and affinity with her people."
The Goldies will be auctioned alongside a rare collection of samples from the long-lost Pink and White Terraces.
The terraces, described as the "eighth wonder of the world", were situated on the edge of Lake Rotomahana near Rotorua.
They disappeared in 1886 when Mt Tarawera erupted, killing 120 people, burying a village and causing widespread damage.
Part of the terraces were rediscovered in 2011, about 60 metres below the surface of the lake.
The 35 samples of fossilised flora and silica sinter were from the private collection of James Stewart, a civil engineer who was thought to have collected the samples shortly before the eruption.
The collection would be sold as one lot and was estimated to bring $20,000, Mr Thomson said.
"But you can never be sure. There is an incredible interest in this type of offering. In March last year we sold two pieces of the Terraces for $65,000, well above what we expected.
"We had interest from around the world and they were one of the most sought-after things I have ever sold."
The sale next will also features more than 20 paintings and photographs of the Terraces, including The White Terrace by Charles Blomfield, considered the master of terrace portrayal, and a rare 1884 painting by New Zealand artist Joseph Gaut of a Maori woman bathing in the shadow of the Pink Terrace.
Other works in the sale include several by Sir Peter Siddell, one of only two artists knighted in New Zealand.
His 1988 oil, Two Palms, an Auckland cityscape, was predicted to bring $135,000
An unusual oil on two glass panes, Untitled Diptych, by Ralph Hotere, was thought to be his ode to another renowned New Zealand Artist, Colin McCahon. It was expected to bring up to $100,000.
Hotere died earlier this year.
Other artworks being auctioned tonight include pieces by Peter McIntyre, Sir Toss Woollaston, John Gibb, Frances Hodgkins, Evelyn Page, and John Barr Clarke Hoyte.
The auction begins at 6.30pm.
