Blended nanofiber webs of poly(L-lactic acid) (PLLA)/poly(L-lysine) (PLys) with a PLys content of up to 3 % were prepared using an electro-spinning process with trifluoroacetic acid as the spinning solvent, and employed as a substrate for silicification. Silica formation on the surface of the PLLA/PLys nanofibers was carried out by immersing the nanofiber webs in silicic acid solutions at various concentrations for different times. The effects of the silicification conditions and PLys content on silicification were examined by scanning electron microscopy, FT-IR, energy dispersive spectroscopy, and the increase in weight of the substrates. Although the amount of silica formed on the PLLA nanofibers increased with increasing silicification time and silicic acid concentration, the uniformity of the coated layer was not controlled. However, the incorporation of small amounts of PLys in the PLLA nanofibers increased the amount and uniformity of the silica formed on the nanofibers.