Those details led to further revelations in Tuesday's Herald that Mr Smith had earlier written a letter of support for Ms Pullar's medical case while he was ACC Minister.
Last night, Mr Smith - who resigned his portfolios in an emotional statement to Parliament yesterday - said he would not comment on the nature of his relationship with Ms Pullar, "except to say I have a wonderful wife and family who are actually very distressed today, that I have been absolutely loyal to my wonderful wife and I will be to the end of my days".
The Nelson MP said he was not going to get into a commentary over who he had been in relationships with.
"I think many of you may be involved in relationships and if you were required to give evidence and other information and that if 10 years later you were asked how would you describe that person, we don't normally talk about our intimate private lives in public and I think it is quite proper, providing it doesn't change the circumstances, to say that person was a friend."
When Dr Smith met Ms Pullar in the 1990s, she was a volunteer regional communications manager for the party and worked for Enza which did a lot of business in Dr Smith's electorate.
She now works in branding and marketing and has previously been a brand manager at Zespri, a brand consultant at Frucor Beverages and a consultant at Carter Holt Harvey.
In 2001 she was Michelle Boag's publicity manager in her campaign to be party president, and the following year she was campaign manager for MP Pansy Wong.
But her life was changed by her accident in 2002.
Cathy Odgers, writing on her Cactus Kate blog yesterday, said she was with Ms Pullar the night before her accident, which happened as she was going to pick her car up the next day.
"... she took a taxi home and was going back on her bike to pick her car up when [she was] hit on her bike."
ACC has accused Ms Pullar of threatening during a meeting last December to go public with the records she was mistakenly sent unless the corporation gave her two years of benefit entitlement. She has vehemently denied the accusation.
ACC has called in the police to investigate.
The Herald understands Ms Pullar is angry that the focus has moved away from ACC's privacy breach and on to her, her battle with the corporation and her friendship with Dr Smith.
It is understood she accuses ACC of leaking information to the media to shift the story away from what she considers its failings.
Sources told the Herald Ms Pullar's life changed after the accident and although she drifted away from the political scene, she still often discussed her ACC battle with political contacts.
Prime Minister John Key met Ms Pullar when he entered politics, shortly after her accident.
"For a number of years she had mentioned to me, when I was at events, her frustration with ACC, so it was well known," he said this week.
Neighbours at her $700,000 Herne Bay apartment, which she owns with an accountant, were reluctant to comment yesterday.
Auckland Councillor Cameron Brewer last night said he knew Ms Pullar when she was Ms Wong's campaign manager.
"She always seemed very capable, efficient, popular and a really good operator ... she comes from a very good South Island family."
Although the accident "changed her forever" the former Otago University student continued to be a popular person within National Party circles.
It is believed Ms Pullar is in a relationship with the accountant with whom she has she has been living for several years.
