Just lately, catalytic valorization of biomass-driven furfural has attracted nice curiosity. On this work, we report a one-pot photoenzymatic route towards maleic acid (MA) and its C4 derivatives fumaric acid (FA) and D-malic acid (D-MalA) from furfural by cascade catalysis. Xanthine oxidase (XO) in addition to Pseudomonas aeruginosa aldehyde dehydrogenase (PaALDH) was discovered to be a great biocatalyst for the furfural oxidation into 2-furancaboxylic acid (FCA), however the latter displayed a lot larger tolerance towards the enzyme inactivation by reactive oxygen species (ROS) generated by photocatalytic oxygenation. In addition to, the enzyme inactivation could be significantly relieved by entrapping the photocatalyst eosin Y right into a macroporous adsorptive resin NKA-II (EY@NKA). Galactose oxidase M3-5 (GO M3-5) might settle for 5-hydroxy-2(5H)-furanone (HFO) as a substrate, whereas its variants M4 and M5-1 exhibited each larger actions and better stability. Concurrent photoenzymatic manufacturing of MA from FCA was carried out by merging EY@NKA with GO M4/M5-1, with yields of as much as >99%. Nonetheless, simultaneous photoenzymatic conversion of furfural into MA failed, as a result of nice enzyme inactivation. Due to this fact, a temporal compartmentalization technique was utilized for the MA synthesis. A two-step course of incorporating PaALDH, EY@NKA and GO M4/M5-1 was developed for the furfural conversion, resulting in the manufacturing of MA with 94% yield. As well as, the photoenzymatic cascade was facilely prolonged to provide FA and D-MalA by supplementing the corresponding biocatalysts, with 77-82% yields. The current work could pave the best way for sustainable manufacturing of biobased C4 chemical substances.