In this paper, we demonstrate the enhancement of photovoltaic (PV) solar cell efficiency using luminescent silicon nanoparticles (Si-NPs). Sub-10 nm Si-NPs are synthesized via pulsed laser ablation technique. These ultra-small Si nanoparticles exhibit photoluminescence (PL) character tics at 425 and 517 nm upon excitation by ultra-violet (UV) light. Therefore, they can act as secondary light sources that convert high energetic photons to ones at visible range. This downshifting property can be a promising approach to enhance PV performance of the solar cell, regardless of its type. As proof-of-concept, polycrystalline commercial solar cells with an efficiency of ca 10% are coated with these luminescent Si-NPs. The nanoparticle-decorated solar cells exhibit up to 1.64% increase in the external quantum efficiency with respect to the uncoated reference cells. According to spectral photo-responsivity characterizations, the efficiency enhancement is stronger in wavelengths below 550 nm. As expected, this is attributed to downshifting via Si-NPs, which is verified by their PL characteristics. The results presented here can serve as a beacon for future performance enhanced devices in a wide range of applications based on Si-NPs including PVs and LED applications.