Evaporation-induced convective binary assembly of large (A) and small (B) silica nanoparticles is demonstrated as a template-free route to three-dimensionally ordered mesoporous silicas (OMSs), the pore topology of which derives from the interconnected interstices of the resulting ordered nanoparticulate structures. Even without explicit solvent index matching or stabilization (e.g., charge or steric) beyond intrinsic properties of the amino acid nanoparticle synthesis solution, assembly of binary mixtures of silica nanoparticles of ca. 1050 nm in diameter primarily obeys hard-sphere phase behavior despite differences in electrostatic character of the particles. Specifically, the particle size ratio, gamma, governs symmetry of the assemblies among AB(2) and AB(13) phases and enables access of the AB phase. Small-angle X-ray scattering (SAXS) reveals the high yield of ordered binary assemblies and confirms, in combination with transmission electron microscopy, the AlB2, NaZn13, and NaCl crystalline isostructures. Interstitial solid solutions result for the smallest gamma considered (gamma <= 0.3), wherein cubic crystallization of the large particles is templated by interstitially mobile small particles. New mechanistic insight into factors influencing the yield of ordered binary structures includes the degree to which the smaller particles (ca. 1524 nm) within the mixture undergo unary crystallization, as influenced by lysine or other basic amino acids used in the nanoparticle synthesis, as well as matching of the time scales for convective nanoparticle assembly and crystallization. Ultimately, the demonstrated robustness of the binary nanoparticle assembly and the control over silica particle size translate to a facile, template-free approach to OMSs with independently tunable pore topology and pore size.