In this work, we reported the green synthesis of Solanum nigrum extract capped copper oxide nanoparticles (SN@CuO NPs) at room temperature, avoiding harsh, toxic, and environment unfriendly chemicals. The synthesized SN@CuO NPs, were analyzed with the help of spectroscopic techniques. UV-visible spectroscopy confirmed the synthesis of SN@CuO NPs in reaction mixture while fourier transform infrared spectroscopy (FTIR) results revealed capping of phytochemicals of Solanum nigrum over the surface of CuO NPs. Morphology and elemental composition of formed SN@CuO NPs were explored with the help of FE-SEM, TEM, and EDS, respectively. Crystalline nature, surface charge and specific surface area was characterized using XRD pattern, DLS and BET analyses, respectivley. The data obtained from spectroscopic analyses specified the formation of mesoporous, positively charged and highly stabilized CuO nanoparticles due to adsorption of phytochemicals present in Solanum nigrum leaf extract on the CuO nanoparticle’s surface. SN@CuO NPs have shown promising catalytic activity towards reduction of highly carcinogenic dye Congo red making use of sodium borohydride. Negatively charged reactants like anionic Congo red molecules and BH4− ions eagerly adsorbed on positively charged, small sizes (5–6 nm), mesoporous SN@CuO NPs surface having wide surface area. It is proposed that BH4− ions interacted with SN@CuO NPs to form Cu tetrahydroborates dihydrogen bonded (DHB) tetrahedral L2Cu(ɳ2-BH4) complex, which is proved as an effective reducing agent. This complex acts as dihydrogen source for rapid reduction of azo bond. UV-visible, FTIR, 1H NMR, 13C NMR, and LC-MS studies of reaction mixture at different reaction stages have shown that the major degradation intermediates were benzidine and α-naphthol. The apparent rate constants for the products at intermediate and final degradation stages have been found to be 0.468 min− 1 and 0.0189 min− 1, respectively. A plausible degradation mechanism for Congo red reduction has also been proposed in this study.