A quantitative polarized Raman analysis of ferroelectric grain/domain orientation in LiSbO3 (LS-modified) (K0.5Na0.5)NbO3 (KNN) ceramics is presented, based on the analysis of the complex orientation dependence in space of their Raman-active modes. Complete sets of Raman tensor elements of Ag, and Eg phonon modes for orthorhombic/tetragonal structures of KNN have been determined. Through this spectroscopic algorithm, quantitative information could be extracted in terms of three Euler angles in space for KNN samples consisting of mixed phases, thus enabling quantitative visualization of the local distribution of grains/domains in the solid angle. As an application of the method, we quantitatively examined the unknown crystallographic grain orientation patterns on the surfaces of pure KNN and of KNN-0.05LS ceramics. These two samples were useful to clarify a polymorphic phase transition from the orthorhombic to the tetragonal phase taking place in the LS-modified KNN system. Thus, we demonstrated that polarized Raman spectroscopy is a valuable and efficient tool for nondestructive three-dimensional assessments of grain/domain orientation in ferroelectric materials with complex polymorphic structures. We believe that the data shown here represent a typical scenario encountered in grain/domain orientation assessments of piezoelectric perovskites. Copyright © 2012 John Wiley & Sons, Ltd.