Two modifications of CePdZn have been synthesized and structurally characterized. The high-temperature (HT) β-CePdZn modification forms upon quenching from the melt. The β-CePdZn structure adopts the orthorhombic TiNiSi type and transforms to the low-temperature (LT) α-CePdZn modification (ZrNiAl type) upon annealing at 1080 K. Both modifications have been studied by X-ray powder and single crystal data: P6¯2m, a = 740.4(1), c = 402.18(5) pm, wR₂ = 0.0427, 237 F² values and 14 variables for α-CePdZn and Pnma, a = 707.2(2), b = 441.4(2), c = 806.3(3) pm, wR₂ = 0.0827, 469 F² values and 20 variables for β-CePdZn. The palladium and zinc atoms build up three-dimensional [PdZn] networks in both modifications which leave channels for the cerium atoms. Both modifications show stable trivalent cerium. β-CePdZn orders antiferromagnetically at 3.2(1) K while no magnetic ordering has been observed for α-CePdZn down to 2 K. The course of the magnetic data points to stronger Ce(4¦)-Pd(4d) hybridization in α-CePdZn. Electronic structure calculations reveal only small differences between α- and β-CePdZn regarding the total energy and the Ce(4f)Pd(4d) hybridization.