In 1866, Walter followed his brother's lead, moving with his wife Helen to Dunedin, at that time prosperous from the recent Otago gold rush, and founded a photographic business.

The firm proved a major success, with Alfred travelling throughout the country to take landscape photographs while his brother Walter concentrated on portraiture in Dunedin.

Alfred was joined by his younger brother John and employed other talented photographers such as George Moodie and Thomas Muir, while Walter set up an independent studio.

Alfred Burton, in particular, is considered one of 19th-century New Zealand's most notable photographers, and his series of images of Maori in the southwestern North island is of major significance.

Many of the Burton Brothers' works and much of their original equipment were collected by Dunedin photographer and historian Hardwicke Knight, and are now housed in the Museum of New Zealand Te Papa Tongarewa in Wellington.