p-Aminophenol was synthesized by catalytic hydrogenation of p-nitrophenol on Ni nanoparticles prepared by a chemical reduction method using polyamidoamine (PAMAM) dendrimers as templates. The as-prepared Ni nanoparticles were characterized by XRD, LRS, EDS, FTIR, FESEM, HRTEM and N2 sorption analysis. Smaller-sized, better-dispersed and more active Ni nanoparticles can be successfully achieved using PAMAM dendrimers as templates. Analysis results show the as-prepared Ni nanoparticles are pure f.c.c. nickel. In hydrogenation reactions of p-nitrophenol, Ni nanoparticles show higher catalytic activity than that of Ni nanoparticles prepared in the absence of PAMAM dendrimers. The weight ratio of PAMAM/Ni2+ is proved to be an important parameter on the catalytic activity of Ni nanoparticles and the optimal ratio is 15%. The reason proposed for higher catalytic activity of Ni nanoparticles is a combination effect of smaller particle size, better dispersion and more active Ni nanoparticles.