We developed a novel strategy for synthesizing a highly acidic microporous hybrid titanium phosphate material (H-TiPOx) by incorporating 5-aminosalicylic acid (5-ASA) into the titanium phosphate framework. This new H-TiPOx serves as a Brønsted acid catalyst, exhibiting remarkable total surface acidity of 5.9 mmol g-1 and it efficiently catalyzes the acetalization of abundant biomass derived glycerol to solketal with over 99% selectivity.