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[Display omitted] • SPNC with Cu 2 O/Cu(OH) 2 surface and (1 3 ¯ 2) high-index facet is successfully synthesized. • SPNC shows 31.10 m2 g−1 for surface area and successfully catalyze CO 2 RR. • SPNC shows remarkable selectivity (FE C2H4 = 55.3 %) for the production of C 2 H 4. • Cu 2 O/Cu(OH) 2 surface impact significantly on CO-CO dimer for production of C 2 H 4. In the production of C 2 H 4, a vital raw material in the synthesis of polyethylene and polyvinyl chloride, Cu 2 O is a highly promising catalyst with excellent Faradaic efficiency and selectivity. We propose a method involving the partial reduction of Cu(OH) 2 to Cu 2 O by sodium L-ascorbate for the synthesis of spherical and porous Cu 2 O nanocages (SPNCs) with a surface containing both Cu 2 O and Cu(OH) 2. High-resolution transmission electron microscopy and electron diffraction measurements revealed ∼ 3-nm pores and a (1 3 ¯ 2) high-index facet on the SPNC, respectively. As SPNCs have a porous structure, their specific surface area is greater (31.10 m2 g−1) than that (6.35 m2 g−1) of spherical Cu 2 O nanocrystals (SNCs) with solid interiors. Furthermore, SPNCs, when applied as electrocatalysts for catalysing the CO 2 reduction reaction (CO 2 RR), demonstrated remarkable mass activities (16.92 mA mg−1 at −1.15 V vs. reversible hydrogen electrode) for C 2 H 4 production, with a Faraday efficiency reaching an impressive 55.3 %. Stability test data showed a consistent CO 2 RR current density over 6 h, owing to the porous structure and the presence of both Cu(OH) 2 and Cu 2 O on the catalyst surface. Our proposed SPNC catalysts can be employed as effective CO 2 RR catalysts for producing C 2 H 4 , which may help in reducing the present reliance on petrochemical processes. [ABSTRACT FROM AUTHOR]