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.