The river rises in a black marshy dambo in dense undulating miombo woodland 50 kilometres (31 mi) north of Mwinilunga and 20 kilometres (12 mi) south of Ikelenge in the Ikelenge District of North-Western Province, Zambia at about 1,524 metres (5,000 ft) above sea level.
The area around the source is a national monument, forest reserve and Important Bird Area. Eastward of the source, the watershed between the Congo and Zambezi basins is a well-marked belt of high ground, running nearly east-west and falling abruptly to the north and south.
This distinctly cuts off the basin of the Lualaba (the main branch of the upper Congo) from that of the Zambezi. In the neighborhood of the source the watershed is not as clearly defined, but the two river systems do not connect. The region drained by the Zambezi is a vast broken-edged plateau 900–1200 m high, composed in the remote interior of metamorphic beds and fringed with the igneous rocks of the Victoria Falls. At Shupanga, on the lower Zambezi, thin strata of grey and yellow sandstones, with an occasional band of limestone, crop out on the bed of the river in the dry season, and these persist beyond Tete, where they are associated with extensive seams of coal. Coal is also found in the district just below Victoria Falls. Gold-bearing rocks occur in several places.