Copper-to-copper (Cu–Cu) bonding is a key technology for enabling multi-chip stacking in three-dimensional integrated circuits (3D ICs). Among various bonding methods, thermal compression bonding is the most commonly used technique for forming reliable Cu–Cu joints. However, reducing the bonding temperature while maintaining high bonding quality remains a major challenge, particularly for thermally sensitive devices. Due to the size-dependent properties of metal nanostructures, their sintering temperatures are significantly lower than those of bulk materials, making them attractive as bonding interlayers. Copper nanowire arrays (Cu NWAs) are especially promising due to their excellent electrical, thermal, and mechanical performance. Nevertheless, their tendency to oxidize in air increases the overall process complexity. In this study, Cu NWAs with an average diameter of 177.7 nm were fabricated on copper substrates using template-assisted electrodeposition. The effects of three organic solvents, namely glycerol, ethylene glycol (EG), and polyethylene glycol (PEG), on the heating behavior of Cu NWAs in ambient air were systematically investigated. Glycerol demonstrated superior antioxidant and reducing properties. Through glycerol-assisted sintering at 210°C for 15 min in air under a pressure of 7.59 MPa, Cu–Cu joints with an average shear strength of 20.41 MPa were obtained. However, as the bonding pressure increased from 20 MPa to 40 MPa, the shear strength decreased. Coarsening of nanowires was observed when the sintering temperature was increased to 230°C. In contrast, without glycerol protection, nanowires were found to transform into nanotubes. This work provides a feasible route for low-temperature Cu–Cu bonding in ambient conditions, which could support the advancement of interconnects in 3D ICs.