Tubular nanocomposites of silver nanoparticles (AgNPs)/silica nanotubes (SNTs) with the nearly uniform diameters of 250–350 nm were successfully fabricated by combining the single capillary electrospinning technique (for SNTs as the supports) and an in situreduction approach (for AgNPs). The highly dispersed AgNPs assembled on the inner and outer surface of SNTs through the in situreduction of Ag⁺ by Sn²⁺ ions were confirmed by transmission electron microscopy (TEM), UV-Vis absorption spectra and X-ray photoelectron spectroscopy (XPS). It was interesting to note that the size of AgNPs on the surface of SNTs could be controlled by appropriately adjusting the amount of ammonia solution during the above in situreduction reaction. The catalytic activities of the as-prepared tubular nanocomposites were evaluated by using a model reaction based on the reduction process of 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) in the presence of NaBH₄ as the reductant. The results indicated that all the tubular nanocomposites catalysts with high specific surface area (185–250 m² g⁻¹) exhibited excellent catalytic activities because the highly dispersed AgNPs were exposed on the inner and outer surface of electrospun SNTs, allowing effective contact with the reactants and catalysis of the reaction. In particular, the tubular nanocomposite catalysts containing small size AgNPs had higher catalytic activities than those containing the large size ones, which was attributed to the size-dependent Ag redox potential and surface-to-volume ratio influencing interfacial electron transfer from AgNPs surface to 4-NP in the presence of highly electron injecting BH₄⁻ ions. Those tubular catalysts based on AgNPs/SNTs nanocomposites could be easily recycled without a decrease of the catalytic activities due to their one-dimensional nanostructural property.