5Cr-0.5Mo steel was coated by hot-dipping in a molten Al-10 wt.% Si bath at 700 degrees C for 10, 60, 120 or 180 s. The identification of the phases in the Fe-Al-Si intermetallic phases formed in the aluminide layers during hot-dipping was carried out by using a combination of scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and electron backscatter diffraction (EBSD). The EDS results show a tau(5(H))-Al7Fe2Si phase, which exhibited 2 distinct morphologies, small particles widely dispersed and a continuous layer. Also revealed by EDS were tau(6)-Al4FeSi and tau(4)-Al3FeSi2 phases, which showed plate-shaped morphology, in an Al-Si topcoat. However, the XRD results show the intermetallic phases in the aluminide layer were composed of outer cubic tau(5(C))-Al-7( Fe, Cr)(2)Si and inner hexagonal tau(5(H))-Al7Fe2Si. EBSPs and mapping functions in EBSD helped to clarify the confused phase identifications yielded by EDS and XRD. In this way, the small intermetallic particles and the continuous intermetallic layer were identified as cubic tau(5(C))-Al-7(Fe, Cr)(2)Si and hexagonal tau(5(H))-Al7Fe2Si, respectively, and the plate-shaped intermetallic phase was identified as monoclinic tau(6)-Al4FeSi and tetragonal tau(4)-Al3FeSi2 with the same metallographic morphology. EBSD proved to be a very effective technique for local phase identification of aluminide layers with complicated multiphase morphologies. (C) 2010 Elsevier B.V. All rights reserved.