Measurements of the microstructure commensurate with the viscosity and normal stress differences in shearing colloidal suspensions provides an understanding of how to control the viscosity, shear thinning, and shear thickening rheological behavior typical of concentrated dispersions. In this presentation, I will review some of the experimental methods and key results concerning the micromechanics of colloidal suspension rheology. In particular, colloidal and nanoparticle dispersions can exhibit shear thickening, which is an active area of research with consequences in the materials and chemical industries, as well as an opportunity to engineer novel energy adsorbing materials. A fundamental understanding of shear thickening has been achieved through a combination of model system synthesis, rheological, rheo-optical and rheo-small angle neutron scattering (SANS) measurements, as well as simulation and theory. In particular, the shear-induced self-organization of “hydroclusters” (transient colloid concentration fluctuations) as predicted by Stokesian Dynamics simulations are measured and connected to the suspension rheology. The onset of shear thickening is demonstrated to be understood as a balance of convective, colloidal and hydrodynamic forces and their associated timescales. The limits of shear thickening behavior are also explored at extreme shear rates and stresses, where particle material properties come into play. Although many applications of concentrated suspensions are hindered by shear thickening behavior, novel materials have been developed around shear thickening fluids (STFs). Ballistic, stab and impact resistant flexible composite materials are synthesized from colloidal & nanoparticle shear thickening fluids for applications as protective materials. The rheological investigations and micromechanical modeling serve as a framework for the rational design of STF-based materials to meet specific performance requirements not easily achieved with more conventional materials, as will be discussed.