Chambers was born in Peebles and moved to Edinburgh in 1814 to work in the book-selling trade and soon branched out into printing. He opened his own bookshop in 1819 on Broughton Street, a historical street absorbed by Edinburgh's New Town. He founded the publishing firm of W. & R. Chambers Publishers with his brother, Robert in 1832. He was a keen advocate of popular education and his firm pioneered the use of industrial technologies of publishing to make print available cheaply. With his younger brother, Robert Chambers, he produced books and periodicals of Scottish interest, such as "Gazetteer of Scotland". They also made money in promulgating the many new science discoveries as the modern world emerged from prior modes of thinking in such periodicals as the "Edinburgh Journal". Their publishing business prospered, and in 1859 Chambers founded a museum and art gallery in Peebles. The brothers collaborated on the publication of "Chambers Encyclopaedia" between 1860 and 1868.