The development of novel and effective methods for the activation of methane is fascinating, which offers a promising potential for the sustainable development of chemical industry and the mitigation of greenhouse effect. Here we successfully synthesize two-dimensional (2D) Zr/5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP) ultrathin nanobelts (UNBs) as a high efficiency catalyst for methane (CH₄) oxidation to carbon monoxide (CO). The Co-UNBs show well photo-coupled electrocatalytic performances for CH₄ activation (CO production rates are 0.171 and 8.416 mmol·g⁻¹·h⁻¹ under dark/visible light, respectively). Density functional theory (DFT) calculations were performed to illustrate the mechanism of photoelectrocatalytic process and the high efficiency oxidation of CH₄ to CO. Based on the ultrathin structure and highly efficient catalytic properties, this work provides a prospecting avenue for the design and synthesis of methane oxidation catalyst.