This paper details the synthesis and combustion characteristics of silicon-based nanoenergetic formulations. Silicon nanostructured powder (with a wide variety of morphologies such as nanoparticles, nanowires, and nanotubes) were produced by DC plasma arc discharge route. These nanostructures were passivated with oxygen and hydrogen post-synthesis. Their structural, morphological, and vibrational properties were investigated using X-ray diffractometry, transmission electron microscopy (TEM), nitrogen adsorption-desorption analysis, Fourier transform infrared (FTIR) spectrometry and Raman spectroscopy. The silicon nanostructured powder (fuel) was mixed with varying amounts of sodium perchlorate (NaClO4) nanoparticles (oxidizer) to form nanoenergetic mixtures. The NaClO4 nanoparticles with a size distribution in the range of 540 nm were prepared using surfactant in a mixed solvent system. The combustion characteristics, namely (i) the combustion wave speed and (ii) the pressure-time characteristics, were measured. The observed correlation between the basic material properties and the measured combustion characteristics is presented. These silicon-based nanoenergetic formulations exhibit reduced sensitivity to electrostatic discharge (ESD).