A strong effort has been devoted recently toward processing of metal–ceramic composites with tailored microstructure by colloidal methods. The aim of this work is to optimize the rheological behavior of concentrated Al2O3–nickel (Ni) aqueous suspensions and further slip casting in order to obtain dense green composites. Compositions with Ni relative contents ranging from 5 to 75 vol% were prepared from suspensions with high solids loadings (50 vol%) by adjusting the colloidal stability of each component in terms of pH, mobility, dissolution conditions, and influence of polyelectrolytes. The rheological properties were measured under controlled rate and controlled stress conditions at different basic pH conditions and contents of polyelectrolyte. Better rheological conditions of the mixtures were found for pH 10 and 1.0 wt% polyelectrolyte. Minimum viscosity was obtained for suspensions containing 15 vol% of Ni. The analysis of flow curves demonstrates that the suspensions form a structure at very low shear, hindering sedimentation. Homogeneous slip cast bodies with green densities up to 70% of theoretical and up to 75 vol% Ni were sintered in Ar to achieve dense biphasic composites.