Conditions for the synthesis of aluminum organophosphonate (AOP) and aluminophosphate (AlPO) spheres containing periodic mesopores were optimized and demonstrated to be general morphological controls for the surfactant-assisted synthesis of mesoporous materials. High-quality AOP and AlPO spheres with uniform mesopores were obtained at low and high temperatures, respectively. The aerosol-assisted synthesis of materials with uniform mesopores was categorized by using the difference in relative density of soluble AOP and AlPO oligomers that interact with ethylene oxide (EO) units in EOnPOmEOn triblock copolymer (PO=propylene oxide). Then, ordered mesoporous structures are constructed with the adequate amount of species in resultant frameworks, and the number of interactive points in soluble species determines the resultant density of the frameworks after self-assembly. Consequently, temperature-dependent synthesis, which allows controlled infiltration of soluble species to match the density of resultant frameworks, is required for the formation of ordered mesoporous structures under morphological control.