Amorphous mesoporous aluminophosphates (AlPO) with P/Al molar ratio in the range 0.8-1.15 are synthesized by using the citric acid ( CA) route and are systematically characterized using N-2-adsorption, XRD, SEM, solid-state CP-MAS NMR, FT-IR, TG-DTA, CO2-TPD, and NH3-TPD. The characterization studies show that the change in P/Al ratio could affect the structure, texture, thermal stability, and surface acid-base properties of AlPO. Samples with a relatively low P/Al ratio (<= 1.0) exhibit uniform amorphous mesoporous character and high thermal stability ( up to 1173 K). Partial crystallization of the AlPO framework easily occurred on the sample with higher P/Al ratio (>= 1.1), thus leading to significant decrease of surface area and formation of particle pile mesopores. Both weak acid and weak base sites are observed over AlPO materials, and the amounts of acid-base sites can be effectively controlled by adjusting the P/Al ratio. The presence of suitable interaction between citric acid and AlPO framework is critical for the formation of mesoporous structures. Both CA and PO4 units are considered to be ligands to coordinate with aluminum ions, forming relative uniform complexes ( such as CA-Al- PO4) in the as-synthesized AlPO materials. The mesoporous structure of AlPO materials is obtained after the rapid decomposition of citric acid. Vapor phase selective O-methylation of catechol with methanol reaction is carried out to investigate the catalytic performances of AlPO materials with different P/Al ratios. Among them, AlP(1.)1O shows the highest activity ( 88.4% conversion of catechol) and the highest yield of guaiacol ( 74.3%). The presence of suitable weak acid-base pairs may play an important role on the title reaction.