For the ﬁrst time, MAX phases in the Hf−Al−C system were experimentally synthesized using reactive hot pressing. HfC was observed as the main competing phase. The lattice parameters of Hf2AlC and Hf3AlC2 were determined by Rietveld reﬁnement based on the X-ray diﬀraction data. The atomic stacking sequence was revealed by highresolution scanning transmission electron microscopy. Mixtures of 211 and 312 stacking were observed within the same grain, including 523 layers. This transition in atomic structure is discussed.