A new photocatalytic system involved H2 evolution and CH4 conversion is established. Simultaneous utilizations of electron and hole for two reactions are developed. Synergistic effect between the H2 evolution from H2O and CH4 conversion is achieved. Considerable quantum efficiencies of electron to 4.7% and hole to 3.3% are gained. High-valued product of C2H6 is the main product of CH4 conversion.