MIL-101(Cr)@TiO2 core-shell composite material was synthesized via the hydrothermal method, where MIL-101(Cr) served as the core and TiO2 acted as the shell. SEM results revealed that the metal-organic framework core effectively prevented the aggregation of TiO2 nanoparticles and facilitated their dispersion. Characterization techniques such as XRD, XPS, and TGA were utilized to confirm the successful loading of TiO2 onto MIL-101(Cr) and its excellent thermal stability. MIL-101(Cr)@TiO2 was employed in photocatalytic degradation of dye pollutants and vehicle exhaust, and the potential degradation mechanisms were investigated in detail. The results showed that MIL-101(Cr)@TiO2 exhibited excellent photocatalytic degradation performance towards dye pollutants, with degradation efficiencies of 91.7% and 67.8% achieved for MB and RhB, respectively, under visible light irradiation for 90 min. Furthermore, the photocatalytic degradation of automobile exhaust revealed that the MIL-101(Cr)@TiO2 composite material also exhibited degradation effects on NO, CO, and HC. The degradation efficiency for NO reached 24.2%, indicating its broader applicability.