Abstract: The direct conversion of methane into methanol and other high value-added chemicals with low energy consumption has always been an important goal and major challenge for the sustainable chemical industry. In this paper, a three-dimensional (3D) ZnO/CdS/NiFe layered double hydroxide (LDH) shell/core/hierarchical nanowire arrays(NWAs) structure material was fabricated and utilized for photoelectrocatalytic oxidation of methane at room temperature under simulated sunlight. The results show that the ZnO/CdS/NiFe-LDH photoanode exhibits excellent photoelectrochemical performance and catalytic activity. The photocurrent density under methane atmosphere reaches 6.57 mA cm-2 at 0.9 V (vs. RHE); the yields of methane oxidation products, mainly methanol (CH3OH) and formic acid (HCOOH), catalysed by the synthesized ZnO/CdS/NiFe-LDH composite are 5.0 and 6.3 times those of pure ZnO, respectively. The total Faraday efficiency of the two main products reaches 54.87%. The deposition of CdS nanoparticles (NPs) significantly facilitates the absorption of visible light and promotes the separation of photo-generated carriers. The introduction of NiFe-LDH nanosheets with a three-dimensional porous structure improves the surface reaction kinetics of methane oxidation, acting as an excellent co-catalyst. It also effectively inhibits the production of O2?-, preventing O2?- from further oxidizing methanol and formic acid into CO2, which improves the selectivity of methanol and formic acid. At last, this paper proposes the mechanism of photoelectrocatalytic oxidation of methane to methanol and formic acid over 3D ZnO/CdS/NiFe-LDH composite material, which provides a new idea for the conversion of methane into high-value chemicals with low energy consumption.