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Photocatalysis is an interesting approach to convert solar energy into chemical energy. To achieve efficient energy conversion, a mixed photocatalyst of CaTiO3 nanocuboids and commercial anatase TiO2 nanoparticles P25 were used. This is due to the formation of a heterostructure between CaTiO3 nanocuboids and P25, which enhances the photocatalytic activity. Experiments on the degradation of methylene blue under black light irradiation showed that the hybrid photocatalyst exhibited 11 % higher degradation performance than P25 only. Moreover, a photocatalyst film was formed on FTO glass and used as an electrode for a photoelectrochemical cell (PEC). This is the first time CaTiO3 nanocuboids were mixed with P25 and used as electrodes of PECs.