The strained silicon-bridged [1]ferrocenophane Fe(eta-C5H4)(2)SiBuMe was prepared via a facile chloride substitution reaction at the bridging atom of a readily available SiMeCl-bridged [I]ferrocenophane precursor. Thermal ring-opening polymerization of Fe(eta-C5H4)(2)SiBUMe and Fe(eta-C5H4)(2)SiMe2 afforded polyferrocenyldimethylsilane (PFDMS) and polyferrocenylbutylmethylsilane (PFBMS), respectively. Polyferrocenylsilane nanofibers were fabricated by electrospinning polymer solutions in 90 wt% tetrahydrofuran and 10 wt% N,N-dimethylformamide at room temperature. The effect of,processing parameters such as concentration of polyferrocenylsilanes solution, applied voltage, and working distance on the diameter and morphology of resulting nanofibers were investigated. Electron diffraction patterns from polymer nanofibers revealed that PFS fibers exhibit different orientation owing to variance of the side groups at silicon. (C) 2007 Elsevier Ltd. All rights reserved.