On St. Andrew's Day (30 November) 1870 Webb responded to an appeal from Bishop Robert Gray of Cape Town to accept the Bishopric of Bloemfontein in the interior of South Africa.
One of Webb's first tasks was to oversee the establishment of the Anglican Church on the Diamond Fields in the west of the Diocese of Bloemfontein.
Under Webb the Brotherhood of St Augustine of Hippo grew in strength at Modderpoort in the eastern Free State.
Webb's arrival is referred to as the "era of pacification" and by the end of 1885 he had succeeded in reuniting the divided factions.
[9] Webb was one of the first Anglican bishops to support and nurture corporate women's work in the church through the formation of sisterhoods:[10] The Community of St Michael and All Angels in Bloemfontein and Kimberley (a foremost member being Sister Henrietta); and the Community of the Resurrection of our Lord and St Peter's Home in Grahamstown (under the leadership of Mother Cecile)[9]