Utilizing polymer electrospinning technology, novel electrolyte membranes based on poly(vinylidene fluoride) (PVDF)/organomodified clay (OC)/tripropyleneglycol diacrylate (TPGDA) composite nanofibers with a diameter of 100-400 nm were fabricated for application in lithium batteries. Ultraviolet photo-polymerization of electrospun PVDF/OC/TPGDA nanofibers generated chemically crosslinked TPGDA-grafted PVDF/OC nanofibers exhibiting robust mechanical and electrochemical properties. The prepared fibrous PVDF/OC/TPGDA electrolytes were characterized in terms of morphology, crystallinity, electrochemical stability, ionic conductivity and cell cycleability. Based on differential scanning calorimetry analysis, the crystallinity of PVDF decreased by ca 10% on employing the OC and TPGDA. Compared with pure PVDF film-based electrolyte membranes, the TPGDA- and OC-modified PVDF electrolyte membranes exhibited improved mechanical properties and various electrochemical properties. The OC- and TPGDA-modified microporous membranes are promising candidates for overcoming the drawbacks of the lower mechanical stability of fibrous-type electrolytes with further improvement of electrochemical performance. (C) 2009 Society of Chemical Industry