The pursuit of clean energy generation and environmental preservation is of utmost importance for societal progress. However, couple clean energy production and pollution control is still a difficulty. In this study, a novel electrospun composite mat, with nano zero valent iron (Fe 0 , nZVI) encapsulated into polyacrylonitrile (PAN) nanofibers was acted as a catalyst. The activation energy (E a ) for the hydrolysis of NaBH 4 to produce hydrogen is 22 kJ·mol -1 , hydrogen atom utilization efficiency (HGE) of NaBH 4 is 60.80%. Three kinds of organic dyes 4-nitrophenol (4-NP), methylene blue (MB), and Rhodamine B (RhB) were served as the model pollutant, to construct NaBH 4 -organic system for energy production and pollution reduction. The NaBH 4 -organic system demonstrates a collaborative capability to simultaneously remove organic pollutants and generate hydrogen, with a coupling equilibrium point between the two processes. The hydrogen generation rate (HGR) and HGE increased with the concentration of pollutants increased. The degradation of 4-NP, MB, and RhB followed pseudo-first-order kinetics, with RhB degrading dosage 20 and 44 times higher than 4-NP and MB, respectively. H 2 and H· contributed to the organic degradation. nZVI directly participated in the formation H 2 and H·. PAN@Fe 0 possessed good recyclability and moderate cost. The degradation process adhered to the classical surface reaction controlled Langmuir-Hinshelwood (L-H) model. The integration of synergistic production capacity and pollutant degradation aligns well with the principles of green chemistry and sustainable development. This study demonstrates a novel approach to no precursor loss catalysts preparation, efficient production clean H 2 , advanced treatment of dye-containing wastewater, carbon neutral operation of sewage treatment plant.