A series of zirconocene(IV) halides, [Zr(η-C₅H₄SiMe₃)₂X₂][X = Cl (1) or Br (2)] and [Zr{η-C₅H₃(SiMe₃)₂-1,3}₂X₂][X = F (3), Br (4), I (5), or Cl (6)], has been prepared, either by (i) substitutive procedures from ZrCl₄[involving the following ligand exchanges: Cl^–/C₅H₄SiMe₃^–, Cl^–/C₅H₃(SiMe₃)₂^–, Cl^–/Br^–, Cl^–/l^–, or Cl^–/NMe₂^– followed by NMe₂^–/F^–], or (ii), for complexes (3), (5), or (6), by oxidative addition to [Zr{η-C₅H₃(SiMe₃)₂-1,3}₂(CO)₂]. The only ν_asym(ZrX₂) vibration to be assigned with confidence is for X = F at 563 cm^–1; ¹H and ¹³C n.m.r. data are unexceptional. X-Ray structure determinations of complexes (1)–(5) have been carried out. Their molecular symmetry is close to 2, or crystallographically imposed 2 in (3), with the stereochemistry about the metal centre best described as distorted tetrahedral. The angle X–Zr–X is 93.70(7), 94.2(1), 100.5(3), 100.25(5), and 100.37(4)° for the halides (1)–(5), respectively; and the corresponding centroid–Zr–centroid angles are 129.1, 128.2, 131.4, 131.4, and 131.8°. Metal–halogen distances in (1)[2.505(2) and 2.476(2)Å] and (3)[2.212(6]Å are significantly longer than in the parent zirconocene(IV) halides [Zr(η-C₅H₅)₂X₂](cf. 2.44 Å for X = Cl and 1.98 Å for X = F) as are [by ca. 0.04 Å(average)] the metal–centroid distances in (3)–(5).