Kear was born in Middlesex, the younger daughter of clerk Harold Kear and Constance May née Betteridge. Her brother David became a director-general of the New Zealand Department of Scientific and Industrial Research. She was educated at Walthamstow Hall, Sevenoaks, Caspar Junior College, Wyoming, King's College London and then from 1956 Girton College, Cambridge where she obtained her Ph.D. on the feeding ecology of finches in 1959 under Robert A. Hinde. In 1959 Kear joined the staff of Peter Scott's Wildfowl and Wetlands Trust at Slimbridge, Gloucestershire. Her work included studies to breed Hawaiian goose and the reintroduction captive bred geese into the wild. She examined behaviour and development and made studies on geese grazing. She studied the health of waterfowl and methods for assessing them. From 1974 to 1977 she was the avicultural coordinator at WWT. She married Geoffrey Vernon Townsend Matthews, another researcher at the WWT, in 1964. They separated in 1978.
Kear was the first woman to become vice-president (1989–91), then president (1991–95) of the British Ornithologists' Union, and edited their Ibis magazine from 1980 to 1988. Her books included The Mute Swan (1989), Man And Wildfowl (1990) and Ducks Of The World (1991). Kear was made a fellow of Liverpool University (1978–92) and an honorary doctorate with the title of professor from John Moores University in 1990. She received the British Ornithologists' Union's medal in 1998. She was awarded the Order of the British Empire in 1993.
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