Samantha Brookes on Thursday was accused of giving false evidence about the Rex Newell painting of boats in a harbour.
Ms Brookes had previously described the painting to the Independent Commission Against Corruption (ICAC) as a homestead with a jacaranda tree.
The painting, she said, was given as a birthday present before it was sold by her husband - the former Charlestown MP - to developer Hilton Grugeon in late 2010 for $10,120.
"That's just a big lie, isn't it?" junior counsel assisting Greg O'Mahoney asked.
"There was no painting given to you as a birthday present was there."
Mr Newell earlier told the inquiry he had been approached to paint the picture by Mr Cornwell's father, Brien, to sell at a raffle or to auction off to raise money for Dr Cornwell's 2011 election campaign.
In an often heated exchange, Mr O'Mahoney accused Ms Brookes of lying to the commission during previous sessions.
"On three occasions you have appeared before ICAC and on each occasion you have given testimony laced with lies," Mr O'Mahoney said.
"That is absolutely incorrect," she replied. Ms Brookes also said both Mr Newell and Mr Grugeon gave false evidence about the $10,120 and said the money was not intended for her husband's campaign.
She insists the painting was given to Mr Grugeon as a Christmas present.
Developers have been banned from donating to NSW politics since 2009.
Dr Cornwell told the ICAC he sold it to Mr Grugeon and used the money to pay his tax bill.
Ms Brookes was excused and Dr Cornwell returned to the witness box.
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