A new route for tailoring the behavior of colloidal suspensions through nanoparticle additions is reviewed. Specifically, the interparticle interactions, phase behavior, 3-D structure, and rheological properties of microsphere-nanoparticle mixtures that possess both high charge and size asymmetry are described. Negligibly charged microspheres, which flocculate when suspended alone, undergo a remarkable stabilizing transition upon the addition of highly charged nanoparticles. The formation of a dynamic nanoparticle halo around each colloid induces an effective repulsion between the microspheres that promotes their stability. With increasing nanoparticle concentration, the colloids again undergo flocculation because of the emergence of an effective microsphere attraction, whose magnitude exhibits a quadratic dependence on nanoparticle volume fraction. The broader impact of these observations on colloidal stabilization and assembly of advanced ceramics is highlighted.