We can be sure that the Falls were well known to the native peoples of southern Africa well before any European 'discovered' them. After the San/Bushmen hunter-gatherers, the Tokaleya people inhabited the area, and it was probably they who christened the Falls 'Shongwe'. Later, the Ndebele knew the Falls as the 'aManza Thunqayo', and after that the Makololo referred to them as 'Mosi-oa-Tunya'.

However, their first written description comes to us from Dr David Livingstone, who approached them in November 1855 from the west – from Linyanti, along the Chobe and Zambezi rivers. Livingstone already knew of their existence from the locals, and wrote:

I resolved on the following day to visit the falls of Victoria, called by the natives Mosioatunya, or more anciently Shongwe. Of these we had often heard since we came into the country: indeed one of the questions asked by Sebituane [the chief of the Makololo tribe] travelling was, 'Have you the smoke that sounds in your country?' They did not go near enough to examine them, but, viewing them with awe at a distance, said, in reference to the vapour and noise, 'Mosi oa tunya' (smoke does sound there). It was previously called Shongwe, the meaning of which I could not ascertain. The word for a 'pot' resembles this, and it may mean a seething cauldron; but I am not certain of it.

Livingstone continues to describe the river above the Falls, its islands and their lush vegetation, before making his most famous comment about sightseeing angels, now abused and misquoted by those who write tourist brochures to the area:

Some trees resemble the great spreading oak, others assume the character of our own elms and chestnuts; but no one can imagine the beauty of the view from anything witnessed in England. It had never been seen before by European eyes; but scenes so lovely must have been gazed upon by angels in their flight. The only want felt is that of mountains in the background. The falls are bounded on three sides by ridges 300 or 400 feet in height, which are covered in forest, with the red soil appearing amongst the trees. When about half a mile from the falls, I left the canoe by which we had come down this far, and embarked in a lighter one, with men well acquainted with the rapids, who, by passing down the centre of the stream in the eddies and still places caused by many jutting rocks, brought me to an island situated in the middle of the river, on the edge of the lip over which the water rolls.

From the autobiographical Journeys in southern Africa

Those who bemoan the area's emphasis on tourism should note that there must have been sightseeing boat trips ever since David Livingstone came this way.

Being the most eastern point reachable by boat from the Chobe or Upper Zambezi rivers, the area of the Falls was a natural place for European settlement. Soon more traders, hunters and missionaries came into the area, and by the late 1800s a small European settlement had formed around a ferry crossing called the Old Drift, about 10km upstream from the Falls. However, this was built on low-lying marshy ground near the river, buzzing with mosquitoes, so malaria took many lives.

By 1905 the spectacular Victoria Falls bridge had been completed, linking the copper deposits of the Copperbelt and the coal deposits at Wankie (now Hwange) with a railway line. This, and the malaria, encouraged the settlers to transfer to a site on higher ground, next to the railway line at a place called Constitution Hill. It became the centre of present-day Livingstone, and many of its original buildings are still standing. A small cemetery, the poignant remains of Old Drift, can still be seen on the northern bank of the Zambezi within the Mosi-oa-Tunya National Park.

In 1911 Livingstone became the capital of Northern Rhodesia (now Zambia), which it remained until 1935, when the administration was transferred to Lusaka.