Exploring the interplay between sunlight, semiconducting minerals, and microorganisms in nature has attracted great attention in recent years. Here we report for the first time the investigation of the interaction between a hematite photoelectrode and Pseudomonas aeruginosa PAO1 under visible light irradiation. Hematite is the most abundant mineral on earth, with a band gap of 2.0 eV. A hematite electrode was electrochemically deposited on fluorine-doped tin oxide (FTO). It was thoroughly characterized by environmental scanning electron microscopy (ESEM), Raman, and UV-Vis spectroscopy, and its prompt response to visible light was determined by linear sweep voltammetry (LSV). Notably, under light illumination, the hematite electrode immersed in a live cell culture was able to produce 240% more photocurrent density than that in the abiotic control of the medium, suggesting a photoenhanced extracellular electron transfer process occurring between hematite and PAO1. Different temperatures of LSV measurements showed bioelectrochemical activity in the system. Furthermore, It curves under various conditions demonstrated that both a direct and an indirect electron transferring process occurred between the hematite photoanode and PAO1. Moreover, the indirect electron transferring route was more dominant, which may be mainly attributed to the pyocyanin biosynthesized by PAO1. Our results have expanded our understanding in that in addition to Geobacter and Shewanella it has been shown that more microorganisms are able to perform enhanced extracellular electron transfer with semiconducting minerals under sunlight in nature.