In this work, the pure SnO2 and Cu-doped SnO2 nanoparticles (NPs) were prepared with various Cu doping level (0, 5, 10 and 15 wt%) by employing the co-precipitate method. The study focused to investigating the role of Cu doping on structural, morphological, optical, and electrical properties of SnO2 NPs. The structural pattern confirmed the formation of pure SnO2 NPs, and also the doping of Cu into it. The SEM morphologies appeared as agglomerated larger granules arranged in a random orientation. The TEM images indicate that the nanoparticles are nearly spherical and tend to aggregate into clusters. The XPS spectra confirm the presence of Sn, Cu, O elements, and also the Cu2+ doping into the SnO2 system. The optical bandgap showed an increased absorption value and also a decrease in bandgap with respect to the Cu doping. The FTIR spectra revealed the presence of the Sn–O stretching vibration as well as the O–Sn–O bending vibration and the successful alteration of functional groups by Cu doping. The prepared NPs were used as an n-type layer for the n-SnO2/p-Si and n-Cu@SnO2/p-Si junction diode fabrication. The calculated ideality factor of the diodes decreased continuously with the Cu doping level. Also, the maximum photosensitivity of 960.61% was achieved for 15 of n-Cu@SnO2/p-Si diode due to higher photocurrent. The barrier height values were found to be varied from 0.715 to 0.864 eV. The detectivity (D*) was observed in the range of 109 Jones. Hence, the fabricated n-Cu@SnO2/p-Si diodes will be more suitable for upcoming optoelectronics applications.