The control of the rheological behavior of highly loaded ceramic/polymer suspensions affords the development of near-net shape forming techniques. In this study, suspensions containing sub-micrometer diameter alumina (up to 56 vol%) were fabricated using an anionic dispersant (≈4 vol%) and water-soluble polyvinylpyrrolidone (PVP). The amount and ratio of molecular weights of PVP in the suspension were varied to influence flow behavior. The final pH of the system, ≈9.5, was higher than the isoelectric point (IEP) of alumina implying that the alumina powder possesses a negative surface charge. In the case of alumina at this pH, PVP does not adsorb onto the surface of the powder. The flow behavior of the PVP-containing suspensions displayed yield-pseudoplastic characteristics that closely agreed with the Herschel–Bulkley fluid model. The addition of PVP significantly changed the rheology of the system, increasing the shear yield stress and altering flow behavior. Interparticle interaction approximations of the suspensions were modeled to correlate with experimental observations.