Solar photocatalytic technology is of great significance for adjusting energy structure and environmental improvement. Developing an efficient and lowcost photocatalyst is key to realizing the conversion of solar to chemical energy. In this study, α-Fe 2 O 3-modified few-layer g-C 3 N 4 hybrids (α-Fe 2 O 3 /FL g-C 3 N 4) were successfully prepared by a two-step calcination route with a mixture of α-Fe 2 O 3 and melamine. The samples were characterized by Thermogravimetric analysis, X-ray diffraction, Fourier transform infrared, scanning electron microscope, transmission electron microscope, High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller, UV-Vis absorption spectrum, photoluminescence, and Timeresolved photoluminescence spectroscopy; furthermore, their photoelectrochemical measurements and their photocatalytic performances were evaluated by visible light-driven hydrogen evolution and degradation of RhB. The results showed that the hydrogen production activity and degradation ability of α-Fe 2 O 3 /FL g-C 3 N 4 were significantly enhanced compared with those of α-Fe 2 O 3 /multilayer g-C 3 N 4 (α-Fe 2 O 3 /ML g-C 3 N 4) and FL g-C 3 N 4. The enhanced photoactivities were mainly attributed to the synergistic effect between the increased visible-light absorption, enhanced surface area, and highly efficient electron transfer and separation on the Z-type heterojunction interface. This work not only provides evidence for the formation of FL g-C 3 N 4 nanosheets using a thermal exfoliation method but also provides new insights into the interfacial charge carrier dynamics of Z-scheme α-Fe 2 O 3 /FL g-C 3 N 4 heterostructures for photocatalytic H 2 generation and pollutant degradation.