The pore structure of Cr2O3/Al2O3 catalysts and the surface chemical properties of these pores were characterized by positron lifetime and coincidence Doppler broadening (CDB) measurements. Four lifetime components could be resolved from the positron lifetime spectrum, with two long lifetime components and two short lifetime components. The two long lifetimes τ4 and τ3 are attributed to ortho-positronium (o-Ps) annihilation in large pores and microvoids, respectively. With increasing Cr2O3 content, both τ4 and its intensity I4 show sharp decrease, while τ3 and its intensity I3 keep nearly unchanged. The Doppler broadening S parameters also show sharp decrease with increasing Cr2O3 content. Detailed analysis of the CDB spectrum reveals that the parapositronium (p-Ps) intensity also decreases with increasing Cr2O3 content. This indicates that the change of o-Ps lifetime τ4 is due to the chemical quenching by Cr2O3 but not spin-conversion of positronium. The decrease of o-Ps intensity I4 indicates that Cr2O3 also inhibits positronium formation. The pore structure of Cr2O3 / Al2O3 catalysts and the surface chemical properties of these pores were characterized by positron lifetime and coincidence Doppler broadening (CDB) measurements. Four lifetime components could be resolved from the positron lifetime spectrum, with two long lifetime components and two short lifetime components. The two long lifetimes τ4 and τ3 are attributed to ortho-positronium (o-Ps) annihilation in large pores and microvoids, respectively. With increasing Cr2O3 content, both τ4 and its intensity I4 show sharp decrease, while τ3 and its intensity The analysis of the CDP spectrum reveals that the parapositronium (p-Ps) intensity also decreases with increasing Cr2O3 content. This indicates that the change of o- Ps lifetime τ4 is due to the chemical quenching by Cr2O3 but not spin-conversion of positronium. The decrease of o-Ps intensit y I4 that that Cr2O3 also inhibits positronium formation.