I understand that Iwan Williams, who only joined as managing director a year ago, resigned on Tuesday.
Recruited last year by Mike Clarke, Premier (BSE: PREMIER.BO - news) 's chief executive, Mr Williams is said to have been unhappy that another senior manager, Geoff Eaton, was subsequently drafted in as chief operating officer.
It is unclear whether Mr Williams will receive a payoff but the fact he was not on Premier's board would make it difficult for the company's shareholders to resist any such deal.
Mr Williams had been overseeing Premier's efforts to transform the performance of its bakery division, which includes the Hovis brand.
Premier has become one of the most prominent examples in recent years of debt-laden companies which have been forced into radical restructurings in an effort to stave off collapse.
Under Mr Clarke and his predecessor, Robert Schofield, Premier has sold household name brands such as Quorn, Branston pickle and Hartley's jams.
A Premier spokeswoman said: "Iwan Williams advised the business a while ago that he would like to move on next year to pursue other opportunities."