In this work, a Mo doped CoO nanosheet grown on nickel foam (labeled as: Mo−CoO) with defect‐rich and improved electron transfer capacity was designed to be used as a novel non‐enzyme electrode material. Physical characterizations demonstrated the Mo elements were doped inside of the samples and they were mutually stabilized with each other, resulting in a high structural stability electrochemical catalytical activity even if the content of Mo was low. For non‐enzymatic glucose electrochemical sensing, the prepared Mo−CoO‐1 showed a remarkable sensitivity of 89.3 mA cm−2 mM−1, and a low detection limit of 0.43 μM. Density functional theory (DFT) studies revealed that the doped Mo atom exhibited a higher d‐band center compared to the Co atom. A stronger p‐d orbital hybridization between the glucose and the Mo atoms indicated the enhancement of glucose adsorption and activation. Importantly, Mo−CoO‐1 provided a good selectivity and long‐term stability, which can be expected to be used in future practical applications.