Linda Ross, 57, was sacked as depute headmistress at a Dundee school in 2008 after education bosses discovered the site.
Her husband Vic, 65, set up the site to help stressed teachers, but bosses argued her involvement with www.lindaross.co.uk was "highly inappropriate".
She took Dundee City Council to an employment tribunal to fight the decision to fire her.
Now she faces being struck off the teaching register over allegations of "placing content of an inappropriate nature on a website".
Concerns were raised when adverts started popping up on the site selling X-rated underwear and other adult costumes, including an outfit called "Naughty Schoolgirl".
The site showed a model wearing a see-through crop-top and a plaid miniskirt with a matching tie and gloves.
Other items for sale included a kinky policewoman's outfit, complete with handcuffs.
In an employment hearing in 2008, Mr Ross claimed that he had set up the site to highlight the abuse faced by teachers at the hands of parents and pupils.
It has not been made clear how the adverts came to be placed on the site.
The couple previously courted controversy when Mrs Ross, from Forfar in Angus, was accused of breaking council rules by exposing the pressure teachers were under from parents at the school she worked at in Dundee.
She was told in 2008 that she could keep her job but would be moved to another school. Later the same year she was sacked. Mrs Ross now faces being struck off the teaching register by the General Teaching Council Scotland at a full hearing in February.