William Charles Baldwin worked for a while as a clerk in Liverpool and learned about farming in Scotland before he came to southern Africa where he spent his time travelling, hunting, and trading in ivory. Arriving in Durban in December 1851 he joined a hunting expedition into Zululand early in 1852, during which seven members died of fever and Baldwin's health was permanently affected. After another hunting trip into the same region during 1853 he visited the Cape Colony and Orange Free State early in 1854 to buy horses. He left Zululand in 1857 for the Transvaal and joined a hunting party to Matabeleland. From there he went to Bloemfontein, and in March 1858 started out on a hunting trip into present Botswana, reaching the vicinity of Lake Ngami in July. After returning to Natal to refit he again travelled to Lake Ngami in 1859, via a route north of the Makgadigadi Pans.
His most ambitious journey started from Natal in April 1860. Travelling first to Potchefstroom he eventually reached the Victoria Falls early in August, claiming to be only the second European to do so. His description of the falls, giving their dimensions, was the first reliable account of this natural wonder. He returned to Durban in 1861 and left from there for England the same year. His book, African hunting and adventure from Natal to the Zambesi, including Lake Ngami, the Kalahari desert, etc. from 1852 to 1860 was published in London and New York in 1863 (with two later editions). A French translation appeared in 1868 (with later editions), and a Danish translation in 1864. Thus Baldwin became quite well known - perhaps better than his success as a hunter-explorer warranted. He later undertook two more expeditions, one to Canada and one to Iceland.