A recyclable catalyst of sliver nanoparticles well dispersed in mesoporous silica was successfully synthesized via a straight-forward strategy combining an electrospinning technique with post-calcination. The resulting mats containing silver nanoparticles 10 ± 4 nm in size well dispersed in mesoporous silica fibers of 380 ± 80 nm diameter presented surface plasma resonance of silver nanoparticles at 420 nm. The catalytic behavior of the nanofibers on the reduction of methylene blue and Congo red by NaBH ₄ was tracked and showed that the silver nanoparticles immobilized on the silica nanofiber matrix possessed excellent catalytic properties, which may hold great promise in effective and eco-friendly waste water treatment.