Starpolymers have gained substantial interest in biomedical, adsorbent, and catalyst applications because of their inherent structural uniquity. Notably, the structure and properties can be easily tuned by applying various types of addition reactions and functionalizing each part, including the core, arm, and end of the chains. The current study investigated smart starpolymer photocatalysts based on porphyrin core with amphiphilic arm chains. The porphyrin core was subjected to a photocatalytic reaction; the amphiphilic arm chains were objected to adsorb the reagents along with dispersion in the polar media. The starpolymers with the conventional structure were upgraded to intelligent starpolymers by imbuing them with either light-harvesting or thermosensitive properties. We believe that those led to the high efficiency and recyclable starpolymer photocatalysts.