Within the most mesmerizing materials in the world of optoelectronics, mixed halide perovskites (MHPs) have been distinguished because of the tunability of their optoelectronic properties, balancing both the light-harvesting efficiency and the charge extraction into highly efficient solar devices. This feature has drawn the attention of analogous hot topics as photocatalysis for carrying out more efficiently the degradation of organic compounds. However, the photo-oxidation ability of perovskite depends not only on its excellent light-harvesting properties but also on the surface chemical environment provided during its synthesis. Accordingly, we studied the role of surface chemical states of MHP-based nanocrystals (NCs) synthesized by hot-injection (H-I) and anion-exchange (A-E) approaches on their photocatalytic (PC) activity for the oxidation of β-naphthol as a model system. We concluded that iodide vacancies are the main surface chemical states that facilitate the formation of superoxide ions, O2●–, which are responsible for the PC activity in A-E-MHP. Conversely, the PC performance of H-I-MHP is related to the appropriate balance between band gap and a highly oxidizing valence band. This work offers new insights on the surface properties of MHP related to their catalytic activity in photochemical applications.