Since the dissolution of polyolefins is a chronic problem, melt processing has been tacitly accepted as an obligation. In this work, polypropylene (PP) was modified on molecular level incorporating poly(ethylene glycol) (PEG) as graft segment (PP-g-PEG) in a range of 6 to 9 mol%. Gold nanoparticles were nucleated in the presence of the copolymer chains via redox reaction. The dissolution of the amphiphilic comb-type graft copolymers containing gold nanoparticles (80 nm in diameter) was achieved in toluene and successfully electrospun from its solution. The diameter of composite fibers was in the range from 0.3 to 2.5 mu m. The design of the structurally organized copolymer fiber mats provided a support medium for the nanoparticles enhancing the active surface area for the catalytic applications. The resulting composite fibers exhibited rapid catalytic reduction of methylene blue (MB) dye in the presence of sodium borohydride (NaBH4) compared to corresponding composite cast film.