Charles James Mathews was born in Liverpool. After attending Merchant Taylors' School, Crosby, he was articled as pupil to an architect, and continued for some years nominally to follow this profession. His first public appearance on the stage was made on 7 December 1835, at the Olympic Theatre in London, as George Rattleton in his own play The Humpbacked Lover, and as Tim Topple the Tiger in Leman Rode's Old and Young Stager. In 1838, he married Madame Vestris, then lessee of the Olympic, but neither his management of this theatre, nor subsequently of Covent Garden, nor of the Lyceum Theatre, resulted in pecuniary success, although the introduction of the innovation of scenery more realistic and careful in detail than had hitherto been employed in the theatre was due to his enterprise. In the year of his marriage he visited the U.S., but without receiving a very cordial welcome.
As an actor, he held in England an unrivalled place in his peculiar vein of light eccentric comedy. The easy grace of his manner, and the imperturbable solemnity with which he perpetrated his absurdities, never failed to charm and amuse; his humour was never broad, but always measured and restrained. It was as the leading character in such plays as the Game of Speculation, My Awful Dad, Cool as a Cucumber, Patter versus Clatter, and Little Toddlekins, that he especially excelled. In 1856, Mme Vestris died, and in the following year Mathews again visited the U.S., where in 1858 he married Mrs A. H. Davenport. In 1861, they gave a series of "At Homes" at the Haymarket theatre, which were almost as popular as had been those of the elder Mathews.
Charles James Mathews was one of the few English actors who played in French successfully – his appearance in Paris in 1863 in a French version of Cool as a Cucumber, written by himself, being received with great approbation. He also played there again in 1865 as Sir Charles Coldcream in the original play L'Homme blasé (English version by Boucicault, Used up). After reaching his sixty-sixth year, Mathews set out on a tour round the world, in which was included a third visit to the U.S., and on his return in 1872 he continued to act without interruption till within a few weeks of his death. He made his last appearance in New York at Wallack's theatre on 7 June 1872, in H. J. Byron's Not such a Fool as he Looks. His last appearance in London was at the Opera Comique on 2 June 1877, in The Liar and The Cosy Couple. At Stalybridge he gave his last performance on 8 June 1878, when he played Adonis Evergreen in his own comedy My Awful Dad.