Disclosed are various titanyl phthalocyanine polymorphs such as Type I, Type II, Type III, Type IV, Type Z-1, Type Z-2, and Type X, which phthalocyanines can be prepared by dissolving a titanyl phthalocyanine in a solution of trifluoroacetic acid and a chlorinated hydrocarbon. There is then added to the resulting solution a solvent that will enable precipitation of the titanyl phthalocyanine. Subsequently, the titanyl phthalocyanine product can be separated from the solution by, for example, filtration and the product titanyl phthalocyanine obtained can be washed to remove any residual solvent.