Macroporous silica fibers having spherical cavities were fabricated by electrospinning using the spinning solution prepared from the mixed dispersion of tetraethylorthosilicate (TEOS) and polystyrene nanospheres as precursor and sacrificial templates, respectively, by injection through metallic nozzle. By applying electric field, the electro-spun fibers obtained by evaporation-driven self-assembly were collected on flat substrate or rotating drum, followed by the removal of the templates by calcination. The sound absorption coefficient of the porous fibers was measured by impedance tube, and the measured value was larger than 0.9 at high frequency region of incident waves. The surface of the resulting fibers was modified using fluorine-containing silane coupling agent to produce superhydrophobic fibrous materials to prevent the infiltration of humidity.