A new sol-gel method for the direct synthesis of layered surfactant-expanded zirconium phosphates has been developed by reacting together dodecyltrimethylammonium bromide, orthophosphoric acid (85%), and zirconium tetra-n-propoxide in 1-propanol solution at room temperature. The resulting intercalation compounds have been characterized, and their use as starting materials for preparing gallium-containing porous solids has been evaluated. Surfactant species form a closely packed bilayer inside the phosphate interlayer region with a basal spacing of 33 Angstrom. Gallium oligomeric species have been inserted into the host structure by ion exchange with dodecyltrimethylammonium ions. Upon calcination at 673 K, highly porous gallium(III)-zirconium phosphate composites were formed with Brunauer-Emmett-Teller surface areas between 295 and 366 m(2) g(-1) and narrow pore size distributions. Standard techniques such as thermal programmed desorption of ammonia and pyridine adsorption have revealed their acid nature. These materials show high catalytic activity for the reaction of isopropyl alcohol decomposition at 473 K with conversions and selectivities toward propene nearly 100%.