Electroreduction of carbon dioxide (CO2) to C2 products (ethylene and ethanol) using efficient catalysts is a feasible approach to alleviate the climate crisis. Cuprous oxide nanoparticles (Cu2O NPs) are a promising catalyst for C2 production but suffer from inherent selectivity and durability. To address this challenge, a Cu2O NPs-nitrogen-doped carbon nanotube (Cu2O NPs-NCNT) composite was prepared with carbon nanotubes (CNTs), Cu2O NPs, and phthalocyanine (Pc). The results indicate that Cu2O NPs-NCNT has excellent Faradic efficiency of C2 products (77.61%) at −1.1 V vs RHE, which is 103.43% higher than that of Cu2O NPs. In the potentiostatic electrolysis combined with Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) measurements, Cu2O NPs-NCNT exhibited structural and catalytic current stability over 10 h. Finally, density functional theory calculations combined with XPS demonstrated that the NCNT in Cu2O NPs-NCNT can selectively absorb CO2 through specific N–CO2 interactions. Our work provides a unique strategy to promote the selectivity of Cu2O NPs for C2 production by introducing N-doped linear carbon materials to fabricate composite.