The colloidal microstructure of concentrated suspensions containing anionic comb-polymer-stabilized magnesium oxide (MgO) particles in water was analyzed by shear rheometry for indications of changes in particle microstructure based on particle size and comb-polymer usage. As the suspensions were sheared at different rates, jamming in the sheared MgO suspensions was observed as shear stress overshoots. The shear-induced evolution of the suspension's microstructure was strongly related to the perceived interactions between neighboring MgO particles in the suspension. In the jammed state, interactions are believed to be enhanced by the formation of entanglements between opposing comb-polymer side-chains. Steric repulsion between side-chains was lessened for large particles on account of their diameters, which further enabled side-chain entanglement during close particle contact under shear. Suspensions with relatively wide particle size distributions (0.5–400 μm) were theorized to form hydrocluster aggregates, while suspensions with narrower particle size distributions (0.5–40 μm) most likely resulted in networked microstructures under the influence of the chain entanglements from the adsorbed comb-polymer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40429.