Bismuth oxychloride (BiOCl) is known for its unique layered microstructure, which plays a pivotal role in enhancing its photocatalytic properties. This study introduces a novel strategy for controlling the phase composition, facet orientation, and oxygen vacancy formation in BiOCl through precise pH adjustment during the synthesis. By employing a hydrothermal method, we systematically varied the pH to produce distinct BiOCl phases and conducted detailed structural and photocatalytic analyses. Remarkably, BiOCl synthesized at pH = 7 demonstrated superior photocatalytic activity on rhodamine B (RhB) degradation, which can be attributed to the coexposure of the (001) and (110) facets, as well as an increased concentration of oxygen vacancies. Density functional theory study also revealed that a high concentration of oxygen vacancies leads to enhanced charge separation, which is beneficial for photocatalytic activity. These results indicate that optimizing the pH during synthesis is a viable approach to enhancing the photocatalytic efficiency of BiOCl, offering significant potential for advanced applications in environmental remediation and solar energy conversion.