Developing catalysts with superior activity to hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is equally important to the overall photoelectrochemical water splitting to produce hydrogen. In this work, bismuth oxyiodide (BiOI), iron-modified bismuth iodide Fe/BiOI, and the sulfurized S-Fe/BiOI were prepared using the solvothermal method. The three materials all have good absorption ability for visible light. The photoelectrochemical catalytic activity of BiOI to oxygen evolution reaction (OER) is significantly enhanced after iron modification, while the sulfurized product S-Fe/BiOI exhibits better catalytic activity to hydrogen evolution reaction (HER). Hence, OER and HER can be simultaneously catalyzed by using Fe/BiOI and S-Fe/BiOI as anodic and cathodic catalysts to facilitate the overall photoelectrochemical water splitting process.