Former US Open finalist Pam Shriver claims Romania Fed Cup captain Ilie Nastase - who is banned from his team's tie against Great Britain - made inappropriate comments to her as a teenage star of the women's tour.
Shriver, 54, said Nastase repeatedly asked her if she was a virgin.
"Whenever I saw him at any tournament he would ask me the same question," she told Eyes On Events Radio 5 live's Sportweek.
"This man has not been respectful of women for a long, long time."
The Eyes On Events have contacted the Romanian Tennis Federation for a response, but are yet to receive a reply.
Former world number one Nastase, 70, was expelled from the stadium during Saturday's Fed Cup action after swearing at the umpire, British player Johanna Konta and her captain Anne Keothavong.
Shriver says that although she spoke to friends about the two-time Grand Slam winner's behaviour during the pair's playing days, she did not officially report it.Johanna Konta tears & Nastase sent off - dramatic scenes at Fed Cup
"When I got older, perhaps 20, and he asked me for about the 30th time, I said, 'would you please stop asking me that?'," added Shriver, who won 22 Grand Slam doubles titles.
"Sort of to his credit, he never asked me again. I set a firm boundary and he stopped."
The International Tennis Federation is investigating Nastase's conduct on Saturday and also derogatory comments he made about the unborn child of 23-time Grand Slam singles champion Serena Williams the day before. At the same pre-match media conference, he also asked for the room number of British counterpart Keothavong.
"You want the punishment to match the crime and he behaved really badly," added Shriver.
"I think it has all gone too far. I think it is over now, I think he is done as a coach, certainly in any formal setting.
"Everybody has a couple of different sides to their personality and certainly not all of Ilie Nastase is evil and mean and sexist. But unfortunately he does not have a filter and there is a side that is, so he can't coach women players any more."
American Shriver is a two-time Fed Cup champion, who reached the final of the 1978 US Open as a 16-year-old, losing to Chris Evert.
Britain trail Romania 2-1 in their best-of-five World Group II play-off in Constanta after Konta lost Sunday's opening singles rubber to world number five Simona Halep.Shriver reached the US Open final at the age of 16