ESR spectroscopy was used to investigate paramagnetic sites in sulfated zirconia. Catalysts derived from zirconium oxide and zirconium hydroxide were studied. It was demonstrated that paramagnetic sites assigned to near-surface F-centers were formed during activation at temperatures above 573 K. The catalyst derived from zirconium hydroxide shows after activation at 873 K two types of paramagnetic sites: F-centers and Zr3+ sites. Both F-centers and Zr3+ sites in this catalyst form complexes with reagents upon n-butane or hydrogen adsorption at range of 423-523 K in contrast to paramagnetic sites of the oxide-derived catalyst.