The synthesis of multi-carbon (C₂₊) fuels via electrocatalytic reduction of CO, H₂O using renewable electricity, represents a significant stride in sustainable energy storage and carbon recycling. The foremost challenge in this field is the production of extended-chain carbon compounds (C_n, n ≥ 3), wherein elevated ^*CO coverage (θ_co) and its subsequent multiple-step coupling are both critical. Notwithstanding, there exists a “seesaw” dynamic between intensifying ^*CO adsorption to augment θ_co and surmounting the C-C coupling barrier, which have not been simultaneously realized within a singular catalyst yet. Here, we introduce a facilely synthesized lattice-strain-stabilized nitrogen-doped Cu (LSN-Cu) with abundant defect sites and robust nitrogen integration. The low-coordination sites enhance θ_co and concurrently, the compressive strain substantially fortifies nitrogen dopants on the catalyst surface, promoting C-C coupling activity. The n-propanol formation on the LSN-Cu electrode exhibits a 54% faradaic efficiency and a 29% half-cell energy efficiency. Moreover, within a membrane electrode assembly setup, a stable n-propanol electrosynthesis over 180 h at a total current density of 300 mA cm⁻² is obtained.