The first solid-state synthesis of diamond structure silicon nanocube structures with edge lengths of 8-15 nm is reported. It is well-established that controlled high-temperature processing of hydrogen silsesquioxane produces exceptionally well-defined pseudospherical silicon nanocrystals. However, only a small number of accounts outlining shape-controlled synthesis have appeared. We report here that, upon prolonged annealing in an oxide matrix, nanocrystal surfaces thermodynamically self-optimize, yielding particles with cubic geometries. Surface functionalization of the resulting nanocubes is readily achieved via thermal hydrosilylation. Discussion will include description of the synthetic procedure, comprehensive material characterization, and the factors that lead to the formation of cubic structures.