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Three forms (cis-, trans-, β-trans-) of [Pd(NH3)2Cl2] were obtained as pure single-phase powder materials. Ab initio structure determinations using X-ray powder diffraction were carried out. The cis-Pd(NH3)2Cl2 [a = 6.3121 (2), b = 6.4984 (2), c = 3.3886 (1) Å, α = 96.604 (4), β = 97.290 (4), γ = 104.691 (2)°, Z = 1, space group P1] and trans-Pd(NH3)2Cl2 [a = 6.5398 (3), b = 6.8571 (4), c = 6.3573 (3) Å, α = 103.311 (5), β = 102.454 (3), γ = 100.609 (4)°, Z = 2, space group P] phases have a typical layer-column structure, while β-trans-Pd(NH3)2Cl2 [a = 8.1540 (2), b = 8.1482 (2), c = 7.7945 (1) Å, Z = 4, space group Pbca] is described as a parquet-like layer structure. Both trans phases demonstrate the order-disorder phenomenon. The possible ways of phase transitions are discussed. It is noted that the cis phase can transform into trans in the solid state without destroying the crystal body. Further transformation to β-trans follows through a break up of the crystal body.