Nanoporous inorganic (silica) nanofibres with ultra-high specific surface have been fabricated by electrospinning the blend solutions of poly(vinyl alcohol) (PVA) and colloidal silica nanoparticles, followed by selective removal of the PVA component. The configurations of the composite and inorganic nanofibres were investigated by changing the average silica particle diameters and the concentrations of colloidal silica particles in polymer solutions. After the removal of PVA by calcination, the fibre shape of pure silica particle assembly was maintained. The nanoporous silica fibres were assembled as a porous membrane with a high surface roughness. From the results of Brunauer-Emmett-Teller (BET) measurements, the BET surface area of inorganic silica nanofibrous membranes was increased with the decrease of the particle diameters. The membrane composed of silica particles with diameters of 15 nm showed the largest BET surface area of 270.3 m(2) g(-1) and total pore volume of 0.66 cm(3) g(-1). The physical absorption of methylene blue dye molecules by nanoporous silica membranes was examined using UV-vis spectrometry. Additionally, the porous silica membranes modified with fluoroalkylsilane showed super-hydrophobicity due to their porous structures.