Catalytic transfer hydrogenation (CTH) using Cu nanocatalysts offers significant advantages over direct high-pressure hydrogenation. However, the active hydrogen (H*) in this process exhibits poor adsorption and tends to release H2 readily due to the fully occupied 3d states of Cu. To address this issue, a tubular SnO2 support with electron-accepting ability was selected to host Cu nanoparticles, aiming to optimize the Cu 3d bands. The Cu/SnO2 nanohybrids were prepared through an electrospinning technique, followed by hydrothermal synthesis. As evidenced by X-ray photoelectron spectroscopy (XPS) binding energy shifts and density functional theory (DFT) simulations, some electrons from Cu transferred to SnO2 in the Cu/SnO2 nanohybrids due to their different work functions. Such electron transfer enables the Cu 3d orbitals to lose electrons and alters its valence configuration from 3d10 to 3d10-x, which enhances the adsorption of active H* atoms and thereby inhibits undesirable H2 release. The 15 wt % Cu/SnO2 exhibits improved catalytic hydrogenation of 4-nitrophenol with NaBH4, with an optimal normalized rate constant of 56.98 mg-1 min-1 and a turnover frequency of 4.82 min-1, surpassing most reported catalysts. The enhanced activity is attributed to the optimized electronic states, improved hydrogen adsorption, and the tubular structure of the support. This work might shed light on developing more non-noble metal nanocatalysts for CTH by tuning their d bands with appropriate oxide supports.