Rayner studied painting from the age of fifteen, at first with her father and later with established artist friends of the family such as George Cattermole, Edmund Niemann, David Roberts and Frank Stone. Her first exhibited work, an oil painting entitled The Interior of Haddon Chapel, was shown at the Royal Academy in 1852, the first of a series of oils.
She lived in Chester in the county of Cheshire but travelled extensively, painting British scenes, during the summers in the 1870s and 1880s. Her paintings are very detailed and highly picturesque populated street scenes capturing the "olde worlde" character of British towns and cities in the booming Victorian period. Her paintings are very popular today as prints and on jigsaw puzzles. Around 1910 she moved with her sister to Tunbridge Wells, and later to St Leonards, where she died on 8 October 1924, aged 92.