Solar-driven transformation of biomass and its derivatives has attracted tremendous attention in replacing fossil sources to generate chemicals. Developing high-performance photocatalysts for selective conversion of bio-platform molecules remains a great challenge. Herein, metal-doped photocatalyst was designed for the selective catalysis of biomass derivatives, 5-hydroxymethylfurfural (HMF) was efficiently and controllably converted to 2,5-dicarboxylic furan (DFF) or 5-formyl furantocarboxylic acid (FFCA). In the neutral solution, 64% HMF was converted within 12 h and mainly produced DFF with the selectivity of 74–82%. In 0.5 M Na2CO3 aqueous solution, 30% HMF was converted within 2 h and mainly produced FFCA with the selectivity of 69%. The characterization and photoelectrochemical measurement of photocatalyst showed that the modified material had higher carrier transmission efficiency and better visible light response. The mechanism analysis showed that the photogenerated h+ was the main active specie of the FeOOH/MP, and the introduction of FeOOH inhibited the formation of ˙OH in aqueous solution to realize the highly selective conversion process.