Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO2@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO2@Palygorskite. These dispersed droplets had an average diameter of 20–30 µm and exhibited good time stability. The tight adsorption of TiO2@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO2@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO2 for oil. During the photodegradation process, ·O2− and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO2@Palygorskite was enhanced by about 5 times compared with pure TiO2 under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.