Ceramic suspensions were formulated based on an alumina/plasticized-polymer system. The total polymer volume in suspension was held constant, while the relative amount of high-to-low molecular weight polyvinyl butyral (PVB) in suspension was varied. Experiments were performed to elucidate the effects of polymer molecular weight and distribution on the rheological properties of these casting suspensions as well as on the green microstructure of tape-cast components. The polymer properties affected not only the suspension viscosity at a given shear rate as expected, but also the shear thinning behavior of each suspension. Tapes (thickness ≈250 μm) were cast from these suspensions and their properties were evaluated. Pore volume, a measure of the packing efficiency, was found to depend strongly on the polymer molecular weight and distribution. In addition, preliminary lamination studies revealed that dimensional stability and anisotropy were also affected by the relative amount of high-to-low molecular weight PVB. A direct correlation was shown to exist between the shear thinning behavior of these suspensions and the resulting dimensional anisotropy exhibited by the tapes cast from each of them. These results demonstrate that polymeric aids influence not only the suspension rheology, but the green component microstructure as well, and, hence, are an integral aspect of ceramic processing.