Nickel nanoparticles (Ni-NPs) were prepared by thermal decomposition method using Trioctylphosphine (TOP) and Oleylamine (OA). The average particle size (D) estimated from X-ray diffraction (XRD) using Scherrer equation, to be 1-10nm, systematically decreases with increasing concentration of TOP at constant OA concentration. The observed thermopower strongly depends on particle size particularly at low temperatures reaching a very high value of similar to 10(5) mu V/K (at 20 K), and is attributed to the enhanced grain-boundary scattering combined with quantum confinement.