Stable electrodes are crucial for the practical applications of electrochemical systems. In this study, we report a simple method for synthesizing three-dimensional glassy-like carbon (3D & sdot;GC) on an alumina substrate through pyrolysis of benzyl alcohol and applying it to electrocatalytic reactions. Given its distinctive 3D morphology and stability in aqueous solution, the 3D & sdot;GC electrode exhibits significantly higher electrocatalytic activity than the commercial GC. Moreover, the rough surface of the 3D & sdot;GC electrode is favorable for direct immobilization of catalytic sites, such as metals (Au and Ag) and single-atom catalysts. The developed method for immobilizing single Ni sites is successfully applied to the 3D & sdot;GC electrode, resulting in the Ni SAC-3D & sdot;GC electrode that exhibits high CO selectivity and durability for electrochemical CO2 reduction. The Faradaic efficiency of CO is over 90% across a wide potential range. Due to direct immobilization, the Ni SAC-3D & sdot;GC electrode shows remarkable stability even after multiple reuse cycles, indicating its potential for long-term electrocatalytic applications. To gain an understanding of the mechanism underlying the high CO selectivity during CO2 reduction, the theoretical interactions between the individual Ni sites and the carbon substrate are explored. This theoretical analysis highlights the crucial role of the carbon substrate in stabilizing the COOH intermediate for electrochemical CO2 reduction under neutral conditions.