In this paper, in situ Raman spectra of Ta2AlC are measured in the temperature range of 80–500 K at ambient pressure. The frequencies of the Raman modes decrease with increasing temperature, which have been explained by the anharmonic and thermal expansion effects. The line-width of E2g (ω3) mode increases at elevated temperatures, which is found to be due to the anharmonic phonon–phonon scatterings. On the other hand, the line-widths of E2g (ω1) and A1g (ω4) modes decrease continuously with increasing temperature, which is explained by the electron–phonon couplings of these two phonon modes with the Ta 5d electrons. The electron–phonon coupling strengths are obtained both in experiments and density functional calculations. Finally, Ta2AlC is predicted to be a new superconductive MAX phase. Copyright © 2014 John Wiley & Sons, Ltd.