Abstract: Methane bio-oxidation plays an important role in the global methane balance and warming mitigation, while copper has a crucial function in methane biooxidation. On one side, copper is known to be a key factor in regulating the expression of the genes encoding the two forms of methane monooxygenases (MMOs) and is the essential metal element of the particulate methane monooxygenase (pMMO). On the other side, the content and fractionation of copper in the environment have great effects on the distribution of methanotrophs and their metabolic capability of methane and non-methane organic compounds, as well as on the copper-specific uptake systems in methanotrophs. Thus, it is meaningful to know the role of copper in methane bio-oxidation for comprehensive understanding of this process and is valuable for guiding the application of methanotrophs in greenhouse gas removal and pollution remediation. In this paper, the roles of copper in methane oxidation were reviewed, including the effect of copper on methanotrophic community structure and activity, the expression and activity of MMOs as well as the copper uptake systems in methanotrophs. The future studies of copper and methane oxidation were also discussed.