Highly stable poly(N-vinyl-2-pyrrolidone) (PVP) protected copper nanoparticles were prepared using a simple chemical reduction route in different solvents {N, N-dimethyl formamide (DMF) and formamide (FA)} under aerated condition. The particles were characterized using TEM, SEM, XRD, and UV−visible spectroscopic techniques. Copper nanostructures of varying shapes and sizes were obtained using hydrazine hydrate as the reducing agent in both DMF and FA. However, reducing by ascorbic acid in FA leads to formation of mostly spherical copper nanoparticles with a narrow size distribution. The Cu nanoparticles serve as effective catalyst for 1,3-dipolar cycloaddition reactions between terminal alkynes and azides to synthesize 1,2,3-triazoles in excellent yields under mild reaction conditions. The nanocatalysts can be recycled and reused several times without significant loss of their catalytic activity.