In this work, slanted, kinked, and straight silicon nanowires (SiNWs) are fabricated on Si(111) and (100) substrates using a facile two-step metal-assisted chemical etching nanofabrication technique. We systematically investigated the effect of crystallography, morphology of Ag catalyst, and composition of etchant on the etch profile of Ag catalyst on Si(111) and (100) substrates. We found that the movement of AgNPs inside the Si is determined by physiochemical events such as Ag/Ag interaction, Ag/Si contact, and diffusion kinetics. Further, from detailed TEM and micro-Raman spectroscopy analyses, we demonstrate that the metal catalyst moves in the crystallographically preferred etching direction (viz., <100>) only when the interface effect is not predominant. Further, the metal-assisted chemical etching (MACE) system is highly stable at low-concentration plating and etching solutions, but at high concentrations, the system loses its stability and becomes highly random, leading to the movement of Ag catalyst in directions other than ⟨100⟩. In addition, our studies reveal that Ag nanostructures growth on Si(111) and (100) substrates through galvanic displacement is controlled by substrate symmetry and surface bond density. Finally, we demonstrate that by using an optimized balance between the Ag morphology and concentration of the etchant, the angle in slanted SiNWs, kink position in kinked SiNWs, and aspect ratio of straight SiNWs can be controlled judiciously, leading to enhanced optical absorption in the broadband solar spectrum.