Abstract Boron carbide has a wide range of solubility, but the effects of stoichiometry on its microstructure and mechanical response are not well understood. In this study, detailed microstructural characterization was carried out on three hot-pressed B-rich boron carbide samples. Lattice parameter measurements from XRD identified the compositions to be B 4.2 C, B 5.6 C and B 7.6 C. Local substitutional disorder was observed by Raman spectroscopy, particularly for more B-rich samples. Electron energy loss spectroscopy observations suggest that excess boron preferentially substitutes for carbon atoms in the B 11 C icosahedra; after which additional boron modifies the CBC chains. Moreover, the boron content has salient effects on boron carbide densification and microstructure. Improved densification was observed in the more B-rich samples (B 5.6 C and B 7.6 C), and there is a transition from few or no intragranular planar defects (B 4.2 C), to numerous stacking faults (B 5.6 C), to copious twins (B 7.6 C). Nanoindentation experiments revealed that the highest value for B 4.2 C is statistically larger than that for B 5.6 C or B 7.6 C, suggesting that the hardness of boron carbide is reduced by boron substitution.