The crystal structure of the newly synthesized quaternary MAX phase (Cr2/3Ti1/3)3AlC2 was systematically characterized by various techniques. The space group of (Cr2/3Ti1/3)3AlC2 is determined to be P63/mmc by a combination of selected-area and convergent-beam electron diffraction techniques. Rietveld refinements of the neutron diffraction and X-ray diffraction data show that in (Cr2/3Ti1/3)3AlC2, Ti and Cr are ordered with Ti in the 2a and Cr in the 4f Wyckoff sites of a M3AX2 lattice. It is interesting to find that when the order of the magnetic moment of Cr atoms is considered, the ferromagnetic configuration of (Cr2/3Ti1/3)3AlC2 becomes the ground state. Meanwhile, the Raman-active mode wavenumbers of (Cr2/3Ti1/3)3AlC2 were calculated, and the theoretical data are quite consistent with the experimental data, further proving the ordered crystal structure of this phase. The formation of (Cr2/3Ti1/3)3AlC2 with a unique crystal structure may be related to the distinctly different electronegativities and covalent radii of Cr and Ti atoms.