The earliest roots of Methodism in South Molton date back to 1745 – 1754, when John Wesley preached at North Molton and passed through South Molton. The first Methodist Society was formed in 1807 in an old barn opposite Miss Rossiter’s in East Street known as ‘The Rookery Chapel’, albeit some meetings were held in 1806 in a house now at the junction of East Street and Station Road.

By 1821 a replacement chapel was needed for the Rookery Chapel and a new building, with cob walls was erected on the site of the present Hall. It was opened on March 8th 1821.​

In 1882 the foundation stone of the present Duke Street Methodist Church was laid and the building, by Sanders & Son, was completed in 1883 at a total Cost of £1,500. The architect was Mr Lauder.

In 1906, at a cost of £648 the premises were extended. The foundation stone can be seen under the window of Room 7 in the East Car Park adjacent The Manse (Wesley House).​

In 1979-80 there were significant improvements to the interior of the chapel, the rear wall of the gallery was moved in to form a more spacious and welcoming vestibule. At the front some pews were removed, the pulpit altered slightly and an extended platform created with a new communion rail which is removable. Other improvements included new heating and secondary glazing to the outside of the stained glass windows.​

2004 — A major refurbishment of the chapel took place; the pews were replaced by comfortable chairs, the entrance improved by installing fully glazed panels and doors between the vestibule and the main body of the Church, and a complete new Heating system.

Improvements and refurbishment have continued through many years to the adjoining Hall and meeting rooms as well as toilet facilities and access for the Disabled. All of which have made it a welcoming, warm and pleasant place to meet for both Church and the many Community Groups that regularly use the premises.