A new layered oxo-antimony(III) catecholate, [Sb(C6H4O2)](2)O, can be obtained by reacting senarmontite with aqueous catechol. The same reaction performed with valentinite, the other allotropic form of Sb2O3, shows an intermediate hydrate that loses water at about 100 degrees C. Both compounds can be obtained from SbPO4 under appropriate experimental conditions. [Sb(C6H4O2)](2)O and the hydrated form, which appear to be layered materials, have been characterized by X-ray diffraction, thermogravimetric/differential thermal analyses, and infrared techniques. Preliminary evidence of a reversible intercalation of pyridine into [Sb(C6H4O2)](2)O was collected. Taking into consideration the possible use of [Sb(C6H4O2)](2)O and SbPO4 in the held of photocatalysis, their surfaces were studied by scanning electron microscopy.