ABSTRACT Growth of single‐crystal MAX phases is crucial for studying their intrinsic physical properties. Although Ti 3 AlC 2 is one of the most popular MAX phases for the study of high‐temperature structural materials as well as a precursor for MXene, the growth of Ti 3 AlC 2 single crystals remains a challenge owing to the limited solubility of graphite in the Ti melt via the self‐flux method. In this study, a horizontal temperature gradient was used to resolve the dissolution of graphite in the melt and its diffusion rate. Ti 3 AlC 2 single crystals with an area of 9 mm 2 were successfully produced under horizontal temperature gradients. It was tentatively proposed that the crystallinity of Ti 3 AlC 2 single crystals could be reflected by the intensity ratio of the in‐plane and c ‐axial phonon vibration modes in the Raman spectra of the MAX phase.