The town was named by Governor Lachlan Macquarie in 1811 after a small village on the coast of Scotland where his wife was born. One of the first settlers was John Hume, whose son Hamilton Hume became a famous Australian explorer. Hamilton Hume explored the local area and was given a grant of 300 acres of land at Appin as a reward. When he made his famous journey to Victoria with William Hovell in 1824, they started the journey from Appin.