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John Espin, son of William Espin and his wife Sarah Nicholson, Anglican clergyman and educationist, obtained the Bachelor of Arts (BA) degree in mathematics and physical science at Merton College, Cambridge, in 1860. Two years later he was awarded the degree Master of Arts (MA), and was ordained a priest. After teaching at St John's Foundation School in London for some years he and his wife, Catherine Mallam, emigrated to the Cape Colony in 1868. He taught at the Diocesan College (1869–1870) and Zonnebloem College (1870–1874) in Cape Town for some years, but in 1874 moved to Grahamstown, where he became chancellor of the cathedral and theological tutor, while his wife was headmistress of the Diocesan School for Girls. In 1875 the University of the Cape of Good Hope admitted him to the MA degree on the basis of his MA degree from the University of Cambridge. In 1882 he became headmaster of St Andrew's College and during the next 20 years, until his retirement in 1902, developed it into one of the best boys' schools in the colony. It included a flourishing university college department, which made it one of the constituent colleges of the University of the Cape of Good Hope.

Espin was a gentle and unassuming man of impressive scholarship in the religious field and in 1901 Oxford University conferred the degree Doctor of Divinity (DD) upon him. He was also recognised locally as an authority in mathematics, serving as an examiner in this subject for the University of the Cape of Good Hope from 1874 to 1881. His most advanced contribution to the subject was as examiner in algebra and plane coordinate geometry for a single candidate (H.J.L. du Toit*) for the MA degree in Mathematics and Natural Philosophy, in 1878. He also set papers on algebra, arithmetic, plane trigonometry, coordinate geometry, and mechanics for the final examination of the BA degree for several years. From 1894 to his death in 1905 he was a member of the council of the university. When Rhodes University College was established in Grahamstown in 1904 he served briefly as a member of both its council and senate.

Honours and legacy
Espin House at St. Andrew's College, Grahamstown is named in his honour.