Surface functionalization and shape modifications are the key strategies being utilized to overcome the limitations of semiconductors in advanced oxidation processes (AOP). Herein, the uniform α-Fe2O3 nanocrystals (α-Fe2O3-NCs) were effectively synthesized via a simple solvothermal route. Meanwhile, the sulfonic acid functionalization (SAF) and the impregnation of α-Fe2O3-NCs on g-C3N4 (α-Fe2O3-NCs@CN-SAF) were achieved through complete solvent evaporation technique. The surface functionalization of the sulfonic acid group on g-C3N4 accelerates the faster migration of electrons to the surface owing to robust electronegativity. The incorporation of α-Fe2O3-NCs with CN-SAF significantly enhances the optoelectronic properties, ultrafast spatial charge separation, and rapid charge transportation. The α-Fe2O3-HPs@CN-SAF and α-Fe2O3-NPs@CN-SAF nanocomposites attained 97.41% and 93.64% of Cr (VI) photoreduction in 10 min, respectively. The photocatalytic efficiency of α-Fe2O3-NCs@CN-SAF nanocomposite is 2.4 and 2.1 times higher than that of pure g-C3N4 and α-Fe2O3, respectively. Besides, the XPS, PEC and recycling experiments confirm the excellent photo-induced charge separation via Z-scheme heterostructure and cyclic stability of α-Fe2O3-NCs@CN-SAF nanocomposites.