A new quaternary compound PrAlFeNi3 was synthesized and studied by means of X-ray powder diffraction technique. The powder pattern of PrAlFeNi3 was indexed and refined, giving a hexagonal structure, space group P6/mmm (No. 191) with the CaCu5 structure type, a = 5.1132(2) Å, c = 4.0737(1) Å, V = 92.19 Å3, Z = 1, ρx = 7.20 g cm−3, F30 = 173.61 (0.0054, 32) and RIR = 0.77.