A series of $SiO_2$-$TiO_2$ composite sols have been prepared by the hydrolysis of tetraethyl orthosilicate (TEOS) and titanium (IV) isopropoxide dissolved in isopropanol which was controlled by HCl addition. The maximum amount of $TiO_2$ for suitable fiber formation was about 50 mol% in $SiO_2$-$TiO_2$ composite inorganic fibers. The SEM, TEM, and FT-IR results showed that the surface morphology and crystalline phase of the electro spun composite micro/nanoscale $SiO_2$-$TiO_2$ fibers were strongly affected by the content of $TiO_2$ and calcination temperature. The SEM and TEM images reveal that the fibers had diameters varying from hundreds of nanometer to 2 micrometer. The photocatalytic activity of composite inorganic fibers was evaluated by decomposition of methylene blue, acetaldehyde, and formaldehyde in waste water which are recognized as volatile organic compounds (VOCs).