Metal-assisted chemical etching (MACE) has been widely explored for developing silicon (Si)-based energy and optical devices with its benefits for low-cost and large-area fabrication of Si nanostructures of high aspect ratios. Surface structures and properties of Si nanostructures fabricated through MACE are significantly affected by experimental and environmental conditions of etchings. Herein, we showed that surfaces and interfacial energy states of fabricated Si nanowires can be critically affected by oxidants of MACE etching solutions. Surfaces of fabricated Si nanowires are porous and their tips are fully covered with lots of Si nano-sized grains. Strongly increased photoluminescence (PL) intensities, compared to that of the crystalline Si substrate, are observed for MACE-fabricated Si nanowires due to interfacial energy states of Si and SiOx of Si nano-sized grains. These Si grains can be completely removed from the nanowires by an additional etching process of the anisotropic chemical etching (ACE) of Si to taper the nanowires and enhance light trapping of the nanowires. Compared with the MACE-fabricated Si nanowires, ACE-fabricated tapered Si nanowires have similar Raman and PL spectra to those of the crystalline Si substrate, indicating the successful removal of Si grains from the nanowire surfaces by the ACE process.