Since the photocatalytic effect of a single conventional photocatalyst is often not ideal, it is particularly important to design and construct an efficient and stable photocatalyst in a compound way. In this study, we exploited the sol–gel method to combine BiOCl and TiO2 and gave full play to their respective advantages to prepare BiOCl/TiO2 composite materials. Then, X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM) characterization techniques were utilized to study important indicators of composites—composition, morphology, and structure. In the photodegradation experiment of methyl orange (MO), it was found that the photocatalytic performance of 10BTO (the molar ratio of TiO2 to BiOCl is 10:1) was the best among all the composite photocatalysts, and almost complete degradation of MO was realized. Besides, repeated experiments and recyclability tests on composite materials display favorable stability. Through ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS), photoluminescence (PL), transient photocurrent response, electrochemical impedance spectroscopy (EIS), and electron spin resonance (ESR), a possible degradation mechanism is proposed. Given that there are serious environmental pollution problems in our country, we sincerely hope this research will do its best to degrade organic pollutants in wastewater.