Reactions of the acetylacetonate complex [Zr(acac)4] with catechols have been investigated. Two crystalline complexes [Zr3(acac)4(cat)4(MeOH)2] 1 and [Zr(acac)2(DBcat)]22 (H2DBcat = 3,5-di-tert-butylcatechol) are isolated from the respective reactions in toluene, and their solid-state structures established by X-ray diffraction studies. Complex 2 consists of an edge-shared capped trigonal prismatic structure involving two symmetry related [Zr(acac)2(DBcat)] units, while 1 is best visualized as a Zr3 complex, possessing two [Zr(acac)2(cat)(MeOH)] units linked to the central [Zr(cat)2] fragment via four bridging catecholate ligands. Their reactivity was investigated; treatment of 2 with a trace amount of water in a solution of methanol and CH2Cl2 gave a Zr4 oxo complex [Zr4(μ4-O)(acac)4(DBcat)3(OMe)4(MeOH)] 3.