The National Federation of Women's Institute (NFWI) educational work with members before the Second World War made the creation of an adult education college a natural progression for their work. During a residential course at Radnor in 1943, the first plans for an NFWI college were formed. An NFWI conference on Education was held in London the day after the 1945 Annual General Meeting where the creation of a college was formally moved and passed by members. There, the future role and means of teaching within the movement was officially formulated. An Ad Hoc College Committee was established, chaired by Lady Brunner and including Sir Richard Livingstone. It was decided that a residential college with facilities for teaching in the areas of handicrafts, cookery, music and drama, agriculture and general educational subjects. Marcham Park, which had belonged to the RAF during the War, was purchased and renamed Denman College, after Lady Denman who stood down as National Chairman in 1946. The intention was that it should be a focus for the movement's educational activity, though not its sole provider. The Ad Hoc Committee was then dissolved and the Denman College Subcommittee established to deal with the management of the institution. The first Warden, Elizabeth Christmas, was appointed jointly by the Denman College Subcommittee and the General Education subcommittee to run the college in situ, which she continued to do so until her resignation in 1955 due to ill health. It was opened on 24 Sep 1948 by Sir Richard Livingstone and operated as a trust.
The furnishing of the college was undertaken by the counties, with each of the bedrooms decorated in a style that mirrored that of the federation whose name it bore. Initially, the Denman College Subcommittee was responsible for the fabric of the building while the General Education Subcommittee planned the syllabus in relation to the other education services provided by Headquarters through the work of a syllabus group. In 1957, the Denman College Subcommittee took over responsibility for both aspects of the college. In 1974, during the second review of the NFWI committee structure, the functions of the General Education Subcommittee and the educational work of Denman were transferred to a single Education Subcommittee, leaving the maintenance, staffing and running of the college and its grounds to the Denman Management Committee. A working party was set up which produced the report 'On the Future of Education Policy' in 1974 of the movement which moved that the Education Committee's role should be one of co-ordination and stimulation rather than working in isolation. An Education Coordinating Group was set up to allow chairs of all standing committees to discuss their educational work with the aim of rationalising and coordinating their services. The Denman College Subcommittee was dissolved and a liaison officer appointed from the Executive Committee to work with the Principle. In 1985, a financial and staffing crisis was reached in the affairs of the college and a new Denman Management Committee was set up and a 'Save Denman' campaign begun. To the Management Committee was added a Programme Planning Sub-group that included all national sub-committee chairs to advise on future programmes. After the incorporation of the NFWI in 1990, the National Executive Committee of the NFWI became officially the corporate trustees of the new Denman (College) Trust, as they had in practice done since its establishment. The Denman Management Committee continued its work as before but was now answerable to the trustees. In 1996 the NFWI Education and Training Unit was set up through the transfer of several education and training related department from London such as Craft and Home Economics, Voluntary County Organisers (VCOs) training (part), those dealing with accreditation work, Sport and Leisure and Visual and the performing arts in order that they could co-operate more closely with Denman.
By 2005, the area of education was dealt with by the staff of the Denman College, wherein is situated the NFWI Unit. The latter consisted of a crafts and a home economic adviser. They reported to the Education and Federation Support Subcommittee, which had responsibility for the teaching of the core areas of crafts, home economics, music, drama and public speaking in the country.
The structure of the courses remained largely the same since the establishment of the college. 'A' courses dealt with general educational subjects in an introductory fashion and were open to all members, lasting for a day to a week in length. 'B' courses dealt with more specialised subjects in which members were already proficient and wished to improve their skills.