The People's College, Sheffield, was founded by the Rev. Robert Slater Bayley, Minister of Howard Street Chapel, in 1842. Opening in George Street, the College moved in the following year to larger premises in Orchard Street; John Derby was its Secretary in the early years. At that time a large proportion of the poorer children of the nation grew up without the benefit of schooling. Bayley, who in his earlier years in Sheffield had frequently lectured at the Mechanics' Institution, which provided adult instruction in elementary subjects at evening classes, determined to give working youths and young men from the age of 13 upwards the higher education enjoyed by the youth of the leisured classes, for which they would make some payment. It was further decided that young women should be admitted from the outset. The scheme proved popular, and in 1844 fifty classes per week were enrolled. Subjects taught were not only the "Rudimental" Reading, Writing and Arithmetic but, in addition, Geography, Moral Knowledge, English and General History, English Composition, Science, Logic and Algebra, Philosophy and Natural History, English Literature, Latin and Greek. Much of the labour involved fell to Bayley, the College's Principal, though other staff were employed. At first this revolutionary institution stood alone in the country, but its example soon gave rise to similar intitutions elsewhere, notably the Working-Men's College in London which itself gave rise to many imitators.

Bayley was born in Lichfield, probably in 1801, and baptised as an Anglican. After being trained for the Congregational ministry at Hoxton and Highbury Colleges he worked as a minister from June 1828 at Lane End, Longton, Staffordshire, moving in 1830 to the pastorate of the Independent Chapel at Louth, Lincolnshire, where he made his mark by his eloquence, interest in education, and decided views on political questions, amonst which was an abhorrence of war, and where he was one of the founders of the Louth Mechanics' Institute. In 1836 he moved to Sheffield to assume charge of the Howard Street Chapel, in the same year becoming a Fellow of the Society of Antiquaries. Perhaps his strong views led to the schism which developed in 1846 within the Howard Street Chapel congregation, as a result of which Bayley and others seceded but continued to hold services in the People's College. This divisive episode led to a decline in the College's fortunes, and in 1848 Bayley left to take charge of a Congregational Chapel in Ratcliff in the East End of London. He died in Hereford in 1859.

After Bayley left Sheffield the College, on the point of collapse, carried on under a Committee of young enthusiasts under the Chairmanship of Mr Wilson Overend, a prominent physician, for some years with considerable success. By 1870, when Forster's Education Act finally established a national system of education its fortunes were again declining, as other educational institutes were now operating in Sheffield. In 1874 the Corporation ordered the demolition of the Orchard Street premises for new road construction and the College classes were closed, although the Day-school survived until 1878. On 7th May 1879 a farewell gathering of students was held in the Cutler's Hall, the year of the founding of Firth College, an institution which ultimately evolved into the University of Sheffield.