Boron carbide (B₄C) is a ceramic with a structure composed of B₁₂ or B₁₁C icosahedra bonded to each other and to three (C and/or B)-atom chains. Despite its excellent hardness, B₄C fails catastrophically under shock loading, but substituting other elements into lattice sites may change and possibly improve its mechanical properties. Density functional theory calculations of elemental inclusions in the most abundant polytypes of boron carbide, B₁₂-CCC, B₁₂-CBC, and B₁₁C^p-CBC, predict that the preferential substitution site for metallic elements (Be, Mg and Al) is the chain center atom and that for non-metallic elements (N, P and S) it is generally the chain end atom of the three-atom chain in B₄C's rhombohedral crystal lattice. However, Si, a semi-metal, seems to prefer the chain center in B₁₂-CCC and icosahedral polar sites in both B₁₂-CBC and B₁₁C^p-CBC. As a first step to testing the feasibility of elemental substitutions experimentally, Si atoms were incorporated into B₄C at low temperatures (∼200–400 °C) by high-energy ball-milling. High-resolution transmission electron microscopy showed that the Si atoms were uniformly dispersed in the product, and the magnitude of the lattice expansion and Rietveld analysis of the X-ray diffraction data were analyzed to determine the likely sites of Si substitution in B₄C. Further corroborative evidence was obtained from electron spin resonance spectroscopy, magic-angle spinning nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy characterizations of the samples. Thus, a simple, top-down approach to manipulating the chemistry of B₄C is presented with potential for generating materials with tailored properties for a broad range of applications.