The tubular nanocomposite with well-dispersed distribution of small gold nanoparticles (AuNPs) assembled on the inside and outside surfaces of silica nanotubes (SNTs) was fabricated by combining the single capillary electrospinning technique and an in situ reduction approach. The AuNPs/SNTs nanocomposite exhibited a good catalytic activity for reduction of 4-nitrophenol (4-NP).