The rheological behavior and tape-casting performance of ethanol-based Pb(Mg1/3Nb2/3)O3–PbTiO3 (PMN–PT) slurries is studied. A nanocrystalline powder obtained by mechanochemical activation was used. Suspensions were prepared up to solid contents of 32 vol%, significantly higher than those usually reported for nonaqueous systems. The feasibility of replacing toxic solvents commonly used for tape casting of functional ferroelectric materials, often toluene, with ethanol is demonstrated. The density, phases and microstructure of the green tapes and sintered ceramics are presented. Cube-shaped templates were successfully aligned during the tape casting for the processing of 〈001〉-textured PMN–PT ceramics by templated grain growth. An effect of the lamination of tape stacks on the template orientation is described.