Because of their potential applications in catalysis, separation, and gas storage, porous materials such as metal–organic frameworks (MOFs), porous coordination polymers (PCPs), porous organic polymers (POPs), and polymers with intrinsic microporosity (PIMs) have received much attention. Various building blocks have been introduced with various functional groups. Among the various organic building blocks, porphyrin has become one of the most important building blocks for the construction of such materials witnessed by a wide range of molecular architectures using porphyrin derivatives with various applications. In addition, they are often used to modify the surface of porous silica materials such as SBA-15, MCM-41 and MCM-48, because these porous silica materials exhibit narrow pore size distributions, high thermal stability and easy accessibility.In this presentation, a series of highly ordered mesoporous porphyrinosilicas akin to MCM-41 will be discussed, as novel recyclable heterogeneous photocatalysts, demonstrating their efficacy in the selective oxidation. Porphyrins are recognized as efficient photocatalysts for oxidation reactions, attributed to their capacity to generate reactive oxygen species (ROS). Integrating them into a mesoporous silica framework can mitigate self-degradation, thereby yielding an efficient catalytic system with an extended operational lifetime.