We investigated the formation of a nanopyramidal structure and fabricated nanotextured Si solar cells using an Ag metal-assisted chemical etching process. The nanopyramidal structure was formed on a Si flat surface and the nanotexturing process was performed on the p-type microtextured Si surface. The nanostructural formation shows a transition from nanopits and nanopores to nanowires with etching time. The nanotextured surfaces also showed the photoluminescence spectra with an enhanced intensity in the wavelength range of 1,100~1,250 nm. The photoreflectance of the nanotextured Si solar cells was strongly reduced in the wavelength range of 337~596 nm. However, the quantum efficiency is decreased in the nanotextured samples due to the increased nanosurface recombination. The nanotexturing process provides a better p-n junction impedance of the nanotextured cells, resulting in an enhanced shunt resistance and fill factor which in turn renders the possibility of the increased conversion efficiency.