Brough left the Leicester-based business on 31 March, with commercial director Rob Alonso stepping up as acting chief executive.
Alonso has been with the business for 16 years, during which time he has also been IT and operations director.
Speaking to PrintWeek, Brough said his decision was motivated by a desire to explore new opportunities within the mailing industry.
“After 21 years of service, with the last five years as chief executive, I have left the business to pursue further opportunities in the industry,” he said. “During my tenure we saw significant growth and investment at Opus Trust Marketing. I am now looking for a new opportunity and challenge in the industry that I know and love.
“I have no plans as yet other than wishing to stay in the industry in a director role where I can influence strategy.”
Brough will remain a director of the Mail Users’ Association, through which a collective of business mailers work to overcome challenges in the postal market. By its own estimates, the MUA’s membership generates more than 20% of annual postal traffic in the UK.
Working as Opus' chief executive since July 2013, Brough has occupied a number of positions since joining the company as client services manager in November 1996, before moving on to be director of business development and then head of trust post.
One of the last major moves to take place under his watch at Opus was an investment just shy of £2m to buy two Epic Inserting Systems from Pitney Bowes in October last year, while another recent investment saw the circa £20m-turnover firm switch out its Canon cut-sheet colour printers in favour of Ricoh machines in January 2016.
Brough entered the postal sector in 1996 by joining Opus and the Royal Mail from a job as a production manager at the Sheffield premises of vehicle manufacturer Spinflo.
Opus Trust Marketing was unavailable to comment at the time of writing.