Structural features and surface properties of framework zirconium phosphates synthesized via mechanochemical activation (MA) and sol-gel (SG) route were studied using XRD, TEM, P-31 MAS NMR, IR and ESR spectroscopy and compared with their catalytic performance in the reaction of hexane isomerization. A high initial isomerization activity of crystalline zirconium phosphates prepared via MA can be determined by a larger share of the strong Lewis centers probed by TEMPON test molecule.