The structure transitions and phase relationships of DyFe3−xAlx compounds have been investigated by X-ray powder diffraction. Our XRD results show that each of the compounds with x≤0.45 crystallizes in the rhombohedral PuNi3-type structure with space group R3¯m and Z=9; for the 0.8≤x<1.0 compounds, each has a hexagonal structure of the CeNi3 type with space group P63/mmc and Z=6; and each of the samples with 0.45<x<0.8 is a two-phase mixture of the PuNi3- and CeNi3-type structures. The calculated XRD intensities of the DyFe3−xAlx compounds with x=0.2, 0.33, 0.4, and 0.45 indicate that Dy occupies the 3a and 6c sites, Fe and Al distribute randomly on the 18h site, and the 3b and 6c sites are exclusively occupied by Fe, which agrees well with those of our experimental XRD patterns. The XRD intensities of the DyFe3−xAlx compounds with x=0.8 and 1.0 have also been calculated and found to agree with the experimental results with Dy on the 2c and 4f sites, Fe and Al at the 12k site, and Fe at the 2a, 2b, and 2d sites. In the two-phase region with x=0.45–0.8, the values of unit-cell parameters and phase compositions are linearly dependent on the value of x, indicating that the two phases are constituted by the same composition x with different stacking arrangements. This abnormal two-phase equilibrium is further confirmed by the structural analysis of the DyFe2.33Al0.67 (or x=0.67) sample. The samples with x=1.1 and 1.2 were also analyzed, and each found to be a mixture of more than two phases.