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Vertically aligned silicon nanowire (SiNW) arrays have been fabricated over a large area using a silver-assisted single-step electroless wet chemical etching (EWCE) method, which involves the etching of silicon wafers in aqueous hydrofluoric acid (HF) and silver nitrate (AgNO3) solution. A comprehensive systematic investigation on the influence of different parameters, such as the etching time (up to 15 h), solution temperature (10-80 °C), AgNO3 (5-200 mM) and HF (2-22 M) concentrations, and properties of the multi-crystalline silicon (mc-Si) wafers, is presented to establish a relationship of these parameters with the SiNW morphology. A linear dependence of the NW length on the etch time is obtained even at higher temperature (10-50 °C). The activation energy for the formation of SiNWs on Si(100) has been found to be equal to ∼0.51 eV . It has been shown for the first time that the surface area of the Si wafer exposed to the etching solution is an important parameter in determining the etching kinetics in the single-step process. Our results establish that single-step EWCE offers a wide range of parameters by means of which high quality vertical SiNWs can be produced in a very simple and controlled manner. A mechanism for explaining the influence of various parameters on the evolution of the NW structure is discussed. Furthermore, the SiNW arrays have extremely low reflectance (as low as <3% for Si(100) NWs and <12% for mc-Si NWs) compared to ∼35% for the polished surface in the 350-1000 nm wavelength range. The remarkably low reflection surface of SiNW arrays has great potential for use as an effective light absorber material in novel photovoltaic architectures, and other optoelectronic and photonic devices.