Heat-resistant steels of HP series (Fe-25Cr-35Ni) are used as reformer tubes in petrochemical industries. Their composition includes Nb and Ti as strong carbide formers. In the ascast condition, alloys exhibit an austenite matrix with intergranular MC, M23C6 and/or M7C3 eutectic carbides. During exposure at high temperature, phase transformations occur: chromium carbides of M7C3 type transform into the more stable M23C6 type, intragranular M23C6 carbides precipitate, and a silicide, the G-phase (Ni16Nb6Si7), forms due to the instability of MC carbides (NbC). Thermodynamic simulation is of great help for understanding precipitate formation and transformations. Thermo-Calc and Dictra are used to simulate the precipitation of carbides in the austenite matrix during service. However, from an experimental point of view, M23C6 and M7C3 are not easy to distinguish in bulk alloys. Indeed, backscattered scanning electron microscopy does not bring any contrast between the two phases, and energy dispersive spectroscopy (EDS) analysis does not lead to carbon content and consequently to the distinction between M23C6 and M7C3. With transmission electron microscopy (TEM), sample preparation is difficult and the observed area is extremely small. In the present work, HP alloys are investigated by electron backscatter diffraction (EBSD) coupled to EDS. Carbides are identified on the basis of crystal structure, in the bulk, within their microstructural context, and the experimental procedure is both simpler and cheaper than TEM. Precipitates (M23C6, M7C3) could be identified by orientation mapping and single spot analysis.