Published in 1776, the book's full title is An Inquiry Into The Nature and Causes of The Wealth of Nations and explores the division of labour, productivity and free markets.
The edition, expected to fetch between £30,000 and £50,000, was sold to an anonymous telephone bidder after a "fierce competition" at Lyon & Turnbull auctioneers in Edinburgh.
The work by Scottish economist and philosopher Smith reflects on economics at the beginning of the Industrial Revolution and is one of the world's first assessments of what creates wealth within a nation state.
The tract helped earn Smith the label of the 'father of modern economics'.
Simon Vickers, book specialist at Lyon & Turnbull, said: "There was fierce competition from bidders. This is such a significant book in the history of economics; first editions do not readily appear on the market."
The sale was part of an auction of rare books, maps and manuscripts that also saw a letter written and signed by Charlotte Bronte sell for £24,000.