Deactivation of porous photocatalytic materials was studied using three types of microstructured particles: macroporous titania particles, titania microspheres, and porous silica microspheres containing CNTs and TiO2 nanoparticles. All particles were synthesized by emulsion-assisted self-assembly using micron-sized droplets as micro-reactors. During repeated cycles of the photocatalytic decomposition reaction, the non-dimensionalized initial rate constants (a) were estimated as a function of UV irradiation time (t) from experimental kinetics data, and the results were plotted for a regression according to the exponentially decaying equation, α = α 0 exp(-kdt). The retardation constant (kd) was then compared for macroporous titania microparticles with different pore diameters to examine the effect of pore size on photocatalytic deactivation. Nonporous or larger macropores resulted in smaller values of the deactivation constant, indicating that the adsorption of organic materials during the photocatalytic decomposition reaction hinders the generation of active radicals from the titania surface. A similar approach was adopted to evaluate the activation constant of porous silica particles containing CNT and TiO2 nanoparticles to compare the deactivation during recycling of the photocatalyst. As the amount of CNTs increased, the deactivation constant decreased, indicating that the conductive CNTs enhanced the generation of active radicals in the aqueous medium during photocatalytic oxidation.