Caroline Pearson was of considerable financial means, by birth and through marriage. She was daughter of John Lyons of Antigua, who owned St Austin’s, an 190-acre estate in the New Forest, Lymington, Hampshire. She had a sister, Catherine, who is also recorded as an artist; there is a collection of watercolours, depicting her travels between the French Pyrenees and the Alps, in the Radnorshire Museum at Llandrindod Wells. It is likely that the sisters travelled and sketched together. In 1820 Caroline married Henry Shepherd Pearson (1776–1840), who was acting Governor of Penang from 1807 to 1808. When Henry died in 1840 they were residing at Boulogne-sur-Mer in northern France.

Caroline moved in privileged circles and would have associated with influential figures of the day. Her landscape drawings attest to this, with subjects including a view from Lord Brougham's garden at Cannes, and views at M. Haldimand's Lake Geneva.