Charles James was born on 27 April 1880 to William James and Mary Diana Shatford-James at Earls Barton near Broughton, Northamptonshire. His father died when he was six and he was brought up by his mother. He attended school in 
Wellinborough, taking classes through Cambridge University. His father's chemistry books sparked his interest in chemistry, and he built himself a home laboratory when he was 15. He also began a correspondence with renowned chemist William Ramsay, who encouraged his interest and became a life-long mentor to James.
Oxford and Cambridge did not teach chemistry at that time. His family opposed his choice of chemistry as a career, but finally gave way.  In 1899, James went to University College London where he studied under William Ramsay. James won the Ramsay silver medal in 1901.  He passed examinations to become an associate of the Institute of Chemistry in 1904, and a fellow in 1907.