The new type of ion exchanger and solid acid zirconium sulfonated oligo-polystyrenylphosphonate-phosphate (ZSPSP) supported on ZrO2 (ZSPSP/ZrO2) was prepared and characterized by IR, SEM, TG and DSC. The thermal analysis indicated that the ZSPSP/ZrO2 could be used safely below 200degreesC. SEM micrographs demonstrated that ZSPSP/ZrO2 with 1-100 mum of particle diameter was amorphous and microporous structure. Comparing with mineral acids such as H2SO4 and HCl or classical resins such as Amberlyst-15 and Nation NR50 in the esterification reaction between acetic acid and 1-butanol, the order of catalytic activities was: H2SO4 > HCl > ZSPSP/ZrO2 > Amberlyst-15 > Nation NR50. ZSPSP/ZrO2 exhibited higher ion exchange capacities and selectivity for Fe3+, Co2+, Ni2+ and Cu2+ ions than for other ions. (C) 2004 Elsevier B.V. All rights reserved.