As the main component of natural gas, methane is a well-established and widely available feedstock for the production of chemicals, particularly small chain organics. Among them, the electrochemical conversion of methane to liquid fuels is of particular interest, because it can scale up directly with surface area and current density (not volume), typically operates at low temperature, and is capable of achieving efficiencies that are not limited by the Carnot cycle efficiency. Also, electrochemical processes provide a unique opportunity to pair with renewable energy sources, such as wind and solar. In this work, a series of ZrO2-based catalysts are investigated, which exhibit catalytic activity attributed to the strong synergetic effect between ZrO2 and metal oxides (TMO, Fe2O3, Co3O4 and NiO). In contrast to ZrO2@Co3O4 and ZrO2@NiO, the ZrO2@Fe2O3 shows the highest catalytic activity with the largest current density difference at 1.3 V (Δj: 13.65 mA cm-2). Furthermore, these samples show a long-term stability over 200 hours. 1-propanol and 2-propanol are the main product of CH4 partial oxidation after 10 hours under ambient conditions. The density functional theory calculations revealed that the high activity of these ZrO2-based catalysts originated from the optimized charge distribution after the ZrO2 cluster grew on the TMO. The study herein offers more possibilities for the synthesis of higher alcohols by CH4 partial oxidation at room temperature.