Charlotte was born in St Andrew's parish, Edinburgh, one of eleven children, including six daughters, of Alexander Nasmyth,[1][2] the "foremost landscape artist of his day".

[3] Charlotte, in common with her siblings Patrick, Jane, Barbara, Margaret, Elizabeth, and Anne, worked as a studio assistant to her father in Edinburgh, and also taught art classes.

[1][4] After the death of their father in 1840, his legacy and an auction of 155 of the family's paintings gave the Nasmyth sisters financial independence, and enabled them move to England.

[1] Contemporary reviewers described Charlotte's paintings as "little gems",[6][7] "delicious small-room pictures ... meant to .. form the individual treasure of some limited sphere of its own.

[1] A portrait of Charlotte by William Nicholson is in the collection of the National Galleries Scotland,[4] and another by Andrew Geddes[10] is in the British Museum.