Electrospinning is a novel technique used to fabricate nanometers to micrometers diameter polymeric and ceramic fibers. The morphology and structure of fibers which would be dominated by electrospinning process parameters and calcinations conditions are important when considering practical applications. This paper involves an investigation of how heating rate influence morphology and structure of CoFe2O4 nanofibers. The morphology of CoFe2O4 nanofibers changes from a continuous fibrous structure for low heating rate to a winding and packed crystallites nature for high heating rate, increasing heating rate also causes an increase in diameter. FTIR and XRD results demonstrate that PVP/CoFe2O4 composite nanofibers for all heating rate form CoFe2O4 cubic phase with very high crystallinity after calcinations. (C) 2011 Published by Elsevier B.V.