Born in Maidstone, England, to Matilda, née Terry, he was trained as a gardener by his father, George Masters, before moving to Sydney.

Masters began working as a gardener, then collecting insects in Queensland for William John Macleay, with the backing of the zoologist Gerard Krefft, later taking a position with the Australian Museum as an assistant curator.

His expeditions across the eastern states were extended to South and Western Australia, Tasmania, and Lord Howe Island.

[1] Masters made two collections from Australia's south west for the museum in Sydney, noted as exceptional in a period when the study the birds of the region was lacking.

His second expedition (1868–69) was longer and further, journeying from Albany as far as the head of the Pallinup River, returning to Sydney with six more Atrichornis clamosus skins, 10 of Dasyornis longirostris, and eight of Psophodes nigrogularis (western whipbird).