Monodispersed and nano-sized Ni powders were synthesized from aqueous Ni sulfate hexahydrate (NiSO4· 6H2O) inside sucrose as a nonionic polymer network by using wet chemical reduction process. The influence of a nonionic polymer network on the particle size of the Ni powders were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA). The Ni powders obtained by adding of sucrose were nearly spherical in shape and seemed to be nano-sized, typically in the range of 100 nm with not being agglomerated. As the sucrose content increased, the particle size of Ni powders steeply decreased and reached the minimum value, however, the particle size increased again with a further increase of sucrose content. This is believed to be due to the pore size of the swollen polymer network. As a result, the particle size of the Ni powders prepared by the reduction inside polymer network was strongly dependent of the sucrose content.