A range of silica nanofibers with refined mesoporous microstructures were successfully synthesized via the combination of electrospinning and the sol-gel method. It was found that the concentration of nonionic surfactant Pluronic F127 (EO106PO70EO106) significantly influenced the morphology and mesoporous structure of silica nanofiber. With the reduced F127/Tetraethyl orthosilicate (TEOS) mass ratio, from 0.28 to 0.14, the diameter of silica nanofibers decreased from 453 nm to 130 nm, and more importantly, the size and the orientation of the internal mesopores were remarkably regulated. It has therefore been a critical step forward to a new hierarchical silica fiber for modern optical and biomedical applications. (C) 2012 Elsevier B.V. All rights reserved.