The epitaxial organization of nano-objects with different compositions and structures into superlattice nanorods holds great promise for photocatalytic biomass oxidation as it can make full use of sunlight and improve carrier transport efficiency. Here, we construct type II photocatalytic heterojunctions using α-Fe 2 O 3 and Nb 2 O 5 , both of which are alternately grown in situ to form superlattice nanorod structures. Due to the interlaced growth of thin layers of α-Fe 2 O 3 and Nb 2 O 5 , the phase interface between α-Fe 2 O 3 and Nb 2 O 5 is greatly increased, which effectively improves the catalytic activity of the catalyst. The selective oxidation of HMF was achieved by superlattice α-Fe 2 O 3 /Nb 2 O 5 /C nanorod photoelectrocatalysts with 96.6% FDCA selectivity, which was 2.3 times higher than that of α-Fe 2 O 3 and 3.5 times higher than that of Nb 2 O 5 , respectively, and the conversion of HMF was close to 100%. This work provides a new idea for the design of catalysts with superlattice structure and used for biomass conversion.