Immobilization of metal nanoparticles in hollow fiber membranes via alternating adsorption of polyelectrolytes and negatively charged Au nanoparticles yields catalytic reactors with high surface areas. SEM images show that this technique deposits a high density of unaggregated metal nanoparticles both on the surfaces and in the pores of the hollow fibers. Catalytic reduction of 4-nitrophenol with NaBH4, which can be easily monitored by UV–vis spectrophotometry, demonstrates that the nanoparticles in the hollow fiber membrane are highly catalytically active. In a single pass through the membrane, >99% of the 4-nitrophenol is reduced to 4-aminophenol, but this conversion decreases over time. The conversion decline may stem from catalyst fouling caused by by-products of 4-aminophenol oxidation.