Double-atom catalysts (DACs) offer a reasonable and scalable route towards carbon neutrality owing to their efficient catalytic features. However, the challenges associated with the flexibility of their coordination structure usually restrict their full potential as efficient catalysts. Herein, we comprehensively examined the impact of coordination environment regulation on the CO₂R activity of Cu₂-DACs supported on C, N, or B co-doped graphene using ab initio simulations. We highlighted the marked role of the local coordination sphere of Cu₂-DACs in modulating their structural stability and charge transfer characteristics, thereby regulating the adsorption of CO₂ and various reaction characteristics. Notably, boron- and carbon-coordinated Cu₂ centres (Cu₂–B_xC_y) resulted in remarkably strong CO₂ adsorption (−0.65 to −2.31 eV), attributed to their amplified electronic interactions with the CO₂ molecule. The weak CO₂ binding observed on the carbon-nitrogen- and nitrogen-boron-coordinated Cu₂ centres (Cu₂–N_xC_y and Cu₂–N_xB_y) further highlighted the role of the coordination environment in facilitating the versatile binding modes of the key reaction species. The varying CO₂ interactions in these systems were further comprehended and supported by a multilevel descriptor (€) combining both geometric and electronic parameters. This descriptor closely mirrored the DFT results, thereby accentuating its effectiveness as a predictive tool to perfectly model the CO₂ interactions on these catalysts. Moreover, the dynamic behaviour in the adsorption modes led to partial breakdown of the conventional linear scaling relations between the key CO₂ reduction intermediates (*COOH, *CO, and *HCO). Among the numerous types of investigated electrocatalysts, Cu₂–B₅C₁ emerged as a highly active and selective catalyst for methanol production, with a remarkably low limiting potential of −0.54 V, surpassing the performance of several reported Cu-based systems. Besides, our findings underscored the often-overlooked yet crucial role of explicit solvation, which significantly altered both the potential-determining step and product selectivity. These outcomes emphasized the necessity of including solvation effects in realistic electrochemical modelling. Collectively, this study provides a critical mechanistic insight into better understanding the coordination effect on the CO₂R and a robust design strategy for next-generation Cu-based DACs, guiding the development of highly efficient and selective catalysts for CO₂ electroreduction.