<p>The effective separation and utilization of photo-generated carriers are of great significance for promoting the development of photocatalysis, especially in the coupled process of photocatalytic H₂ production and value-added chemicals synthesis. To realize this goal, a sandwich-structured MnO₂@ZnIn₂S₄@Ti₃C₂ hollow sphere was designed and synthesized, in which MnO₂ and Ti₃C₂ were loaded on the inner and outer surfaces of ZnIn₂S₄, respectively. In the photocatalytic system, MnO₂ as oxidation cocatalyst and Ti₃C₂ as reduction cocatalyst can serve as photo-generated holes and electrons collectors, respectively, which boost the photo-generated carrier separation and create a spatially separated redox reaction. Furthermore, the unique hollow structure integrated into the photocatalytic system further endows a significant enhancement in light-harvesting ability. Remarkably, the optimal MnO₂@ZnIn₂S₄@Ti₃C₂ hollow sphere exhibits an outstanding the photocatalytic activity for coupled H₂ production (6.29 mmol g⁻¹ h⁻¹) and selective benzyl alcohol oxidation to benzaldehyde (5.26 mmol g⁻¹ h⁻¹), which is significantly superior to that of ZnIn₂S₄, MnO₂@ZnIn₂S₄, and ZnIn₂S₄@Ti₃C₂. By the <i>in situ</i> irradiated X-ray photoelectron spectroscopy, the result reveals that the spatially separated redox dual-cocatalysts can effectively impel the photo-generated carrier separation. Simultaneously, the intermediates during the benzyl alcohol oxidation process have also been confirmed through <i>in situ</i> electron paramagnetic resonance spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy. This work provides a reference and inspiration for constructing efficient photocatalysts that achieve an efficient coupling of photocatalytic H₂ production and value-added chemicals synthesis.</p>