Pascoe was born in 1782 to James and Anne Willyams. Her father was a banker and partner of the Miner's Bank. The bank had been founded in Cornwall and London in the 1770s by his relation William Lemon MP.
The Willyams family was active in Liberal politics and some were MPs. Pascoe's mother's family were from the Bristol Quaker merchant community. With her sister Jane Louisa Willyams (1786-1878), she wrote a novel, Coquetry, which they published together in 1818 with the help of Walter Scott. She married Reverend Thomas Pascoe, the Vicar of St. Hilary, in 1815.
Her correspondence and writing demonstrated a sustained and self-aware interest in the distinctiveness of Cornwall and a Cornish identity.
See Charlotte McKenzie's chapter on Charlotte Champion Pascoe in her 2021 book Women Writers and Georgian Cornwall.