This work explores the fine microstructural features of B4C-TiB2 composites and suggests an overall microstructure evolution from powder processing to sintering. In addition, small-scale grain structures are correlated to local properties measured by nanoindentation, thus providing trends in mechanical behavior. Dense ceramics were typified by development of a core/shell structure of the boride grains, with the shell comprising a (Ti,W)B2 solid solution with different assemblage and variable amount of W guest cation depending on the processing route. TEM analyses revealed chemical and morphological differences that were associated to the presumed densification mechanisms. Nanoindentation was used to extract the overall and single phase properties of TiB2 core, shell and B4C phase highlighting for the first time hardness and modulus variation as a function of the lattice perturbation, i.e. of nominally pure …