Conversion of methane into high value added chemicals and clean fuels such as methanol under mild conditions is of great importance to the chemical industry. However, traditional thermal catalytic of methane always suffer from harsh reaction conditions and poor product selectivity. Here, we reported photoelectrocatalytic oxidation of methane over BiVO 4 /Au/FeCo–LDH under simulated sunlight illumination with ambient‘ conditions. The results demonstrate that BiVO 4 /Au/FeCo–LDH exhibits excellent photoelectrochemical properties and catalytic activity. The double-layer capacitance ([Formula: see text]) value of BiVO 4 /Au/FeCo–LDH is estimated to be 3.00[Formula: see text]mF[Formula: see text]cm[Formula: see text], indicating its considerable electrochemical active areas. The photocurrent density of BiVO 4 /Au/FeCo–LDH reaches up to 1.46[Formula: see text]mA[Formula: see text]cm[Formula: see text] in methane atmosphere. The methanol yield for photoelectrocatalytic oxidation of methane is 8.46 times that of pure BiVO 4 , and the corresponding Faraday efficiency is 56.09%. Finally, the reaction mechanism of photoelectrocatalytic conversion of methane to methanol based on hydroxyl radical and methyl radical as intermediate products is proposed. Our finding is expected to provide new insight for the design of active and selective catalysts toward photoelectrocatalytic conversion of methane.