Multicomponent Al–Si based casting alloys are used for a variety of engineering applications, including for example, piston alloys. Properties include good castability, high strength, light weight, good wear resistance and low thermal expansion. In order for such alloys to continue operation to increasingly higher temperatures, alloy element modifications are continually being made to further enhance the properties. Improved mechanical and physical properties are strongly dependent upon the morphologies, type and distribution of the second phases, which are in turn a function of alloy composition and cooling rate. The presence of additional elements in the Al–Si alloy system allows many complex intermetallic phases to form, which make characterisation non-trivial. These include, for example, CuAl₂, Al₃Ni₂, Al₇Cu₄Ni, Al₉FeNi and Al₅Cu₂Mg₈Si₆ phases, all of which may have some solubility for additional elements. Identification is often non-trivial due to the fact that some of the phases have either similar crystal structures or only subtle changes in their chemistries. A combination of electron backscatter diffraction (EBSD) and energy dispersive X-ray analysis (EDX) has therefore been used for the identification of the various phases. This paper will present comparisons of phase identification methodologies using EBSD alone, and in combination with chemical information, either directly or through post processing.