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Born in Montrose, the son of a ship's captain, Chalmers was initially apprenticed to a ship's chandler. In 1853, he went to Edinburgh and studied at the Trustees Academy under Robert Scott Lauder alongside William McTaggart who became a close friend. After a short period back in Montrose, he returned to Edinburgh in 1859. He travelled to Brittany in 1862 and visited the Netherlands in 1874 where he met Josef Israels. He is best known for his genre work, usually depicting single figures in interiors. With a shock of red hair contemporary accounts show Chalmers to have been good company and well-liked and respected amongst his peers and students. He died tragically in Edinburgh Royal Infirmary a few days after having been found injured at the foot of a basement stair in North Castle Street. On the evening of the accident, which some considered to have been caused by an assault, either with intent to rob (and he fell by accident) or murder, Chalmers had attended an RSA function after which he had retired with friends to an Edinburgh Club for drinks. He exhibited at the RSA Annual Exhibitions from 1855 until 1878. He became an Associate Member of the RSA 1867 and an Academician in 1871. He served as a Visitor to the RSA Life Class, and following his death his widowed mother established the Chalmers Bursary to provide for an Annual Award to a student in the Life Class.