The Scottish Labour Party's intervention comes days after The Herald revealed that Mr Russell had demanded the resignation of Stow College chairman Kirk Ramsay.
He called on Mr Ramsay to step down after he made a secret recording of a private meeting last month to discuss controversial reforms in the sector between the minister and senior college officials.
Mr Ramsay apologised, but declined to resign and Mr Russell then wrote to every college principal and chairman in the country to highlight his concerns.
Neil Findlay, colleges spokesman for the Scottish Labour Party, has written to the convenor of the Scottish Parliament's education committee.
"Michael Russell has questions to answer on this matter, as it seems a particularly personal attack on a college chair, and an extremely unprofessional way for the person in charge of education in Scotland to carry on," he said. "It also raises further questions regarding the handling and the tone of the regionalisation process in general. This is why it is vitally important to get both gentlemen in to give evidence to throw some light on this whole debacle and to make sure this is not one case of a wider culture of bullying and intimidation within the further education sector."
Liam McArthur, LibDem education spokesman, said: "The Education Secretary's crumbling relationship with the college sector has been laid bare as he would sooner point to concealed bugs attempting to thwart his plans than accept Mr Ramsay's explanation and apology. The Scottish Government's regionalisation plans are going to fail if the Education Secretary continues to treat the sector with suspicion and contempt."
A spokesman for Mr Russell said Mr Ramsay had not asked permission to record any of the meeting's participants.
Mr Ramsay was asked to explain his actions to Mr Russell at the Scottish Parliament.
According to Mr Ramsay, Mr Russell said he was outraged and said he wanted the chairman to resign. Mr Ramsay subsequently apologised.
Mr Russell then issued a letter to others who were at the meeting to express his strong disapproval of Mr Ramsay's actions.
A Scottish Government spokesman said: "[Mr Russell] will consider any request to give evidence from the chair of the committee."