A novel methodology is presented for identifying and distinguishing between structural phases in multi-phasic systems, such as piezoelectric materials like PMN-PT [Pb(Mg1/3Nb2/3)O3-PbTiO3], PIN-PMN-PT [Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3] and PZT [Pb(Zr,Ti)O3], using diffuse multiple scattering and Kossel line diffraction techniques. The method exploits the splitting of triple line intersections from special coplanar reflections combined with logical constraints to generate a splitting fingerprint for robust crystallographic phase determination and discrimination.