The electrochemical conversion of carbon dioxide (CO₂) to methane (CH₄), which can be used not only as fuel but also as a hydrogen carrier, has drawn great attention for use in supporting carbon capture and utilization. The design of active and selective electrocatalysts with exceptional CO₂‐to‐CH₄ conversion efficiency is highly desirable; however, it remains a challenge. Here a molecular tuning strategy−in situ amine functionalization of nitrogen‐doped graphene quantum dots (GQDs) for highly efficient CO₂‐to‐CH₄ conversion is presented. Amine functionalized nitrogen‐doped GQDs achieve a CH₄ Faradic efficiency (FE) of 63% and 46%, respectively, at CH₄ partial current densities of 170 and 258 mA cm⁻², approximating to or even outperforming state‐of‐the‐art Cu‐based electrocatalysts. These GQDs also convert CO₂ to C₂ products mainly including C₂H₄ and C₂H₅OH with a maximum FE of ≈10%. A systematic analysis reveals that the CH₄ yield varies linearly with amine group content, whereas the C₂ production rate is positively dependent on pyridinic N dopant content. This work provides insight into the rational design of carbon catalysts with CO₂‐to‐CH₄ conversion efficiency at the industrially relevant level.