It comes as the group posted a £42m pre-tax loss on the back of falling revenue.
Tuppen has been chief executive of Enterprise for more than 20 years, having founded the business in 1991 before its listing on the London Stock Exchange in 1995.
Under his leadership, Enterprise has grown into one of the largest operators of leased and tenanted pubs in the UK, with a portfolio of about 5,500 properties valued at £4bn.
Following a review of internal and external candidates, the board agreed to appoint Simon Townsend to takeover from Tuppen with effect from 6 February 2014. Townsend joined the business in 1999, was appointed to the board in 2000 and has been chief operating officer for seven years.
Chairman Robert Walker said: "Since founding Enterprise over 20 years ago, Ted has built one of the leading pub companies in the UK. He leaves Enterprise in a strong financial position with improved like-for-like trading and a clear strategy, which is delivering for our publicans and our shareholders."
Tuppen added: "I have thoroughly enjoyed my time at Enterprise and I am immensely proud of what we have achieved. It has been a privilege to work with such a great team of colleagues and I am thankful to them all for their support and hard work over the years. I am confident that under Simon's leadership, the company is in very good hands for the future."
The group also posted its preliminary results for the year ended 30 September 2013 this morning (19 November). Revenue fell by 2.9 per cent from £692m to £639m despite a 0.6 per cent bump in like-for-like net income in the final quarter.
EBITDA before exceptional items stood at £313m, down from £340m in 2012. However, after exceptional costs of £163m, pre-tax profit tumbled from £34m to a loss of £42m.
The exceptional costs are mostly made up of a revaluation of the pub estate and a write down of non-current assets.
"Strong" operational cash generation combined with £150m net proceeds from Enterprise's disposal programme has reduced net debt by £216m to £2.5bn. An unsecured convertible bond issued, raising £97m, also reduced bank debt, net of cash, to £41m, down from £310m.
Ted Tuppen said: "We are pleased to report an improving trend in our trading performance which, together with our actions to improve the quality of the estate and reduce our net debt, puts us on a clear path to return to growth in the near term.
"This performance was particularly pleasing when set against the challenging economic conditions, the adverse weather at the beginning of the year and the failure of our wines and spirits distributor. It is through the tireless efforts of our employees and the great work of our publicans that we have steered the business toward this growth trajectory and have delivered like-for-like net income growth of 0.6 per cent in our final quarter."
Like-for-like net income growth continued into the first seven weeks of the current financial year, Tuppen added.