The acidic properties of aluminum phosphate (AlPO4-5) solid acid catalyst were characterized by temperature programmed desorption (TPD) of ammonia (NH3), n-propylamine (n-C3H7NH2), iso-propylamine [(CH3)(2)CHNH2] and n-dipropylamine [(C3H7)(2)NH] separately, and its catalytic performance in benzene alkylation with long chain olefin was studied in a fixed-bed reactor. The characterized acid amount of catalyst increased with the basicity of adsorbates. With increase of the activation temperature of catalyst, the acid amount characterized by NH3-TPD decreased, however, it increased when characterized by TPD using three other adsorbates. The desorption kinetics of TPD process and the deactivation kinetics of catalyst were investigated. The acidity and catalytic performance of catalyst was also correlated. The results showed that the acid amount and strength are well correlated with the activity and stability using NH3 as adsorbate, respectively, which indicated NH3 was a better basic adsorbate. It was also found that the catalyst with higher acid amount and lower acid strength on the surface exhibited the better catalytic performance and stability.