Cobalt chloride (CoCl(2))/poly(ethylene oxide) (PEO) hybrid nanofibers with diameters ranging from 500 to 700 nm were successfully synthesized by a simple and versatile approach of electrospinning. The CoCl(2)/PEO hybrid nanofibers were studied by different techniques such as Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Fourier Transform Infrared (FTIR) and Thermogravimetric Analysis (TGA). One dimensional (1-D) surface roughness average (Ra(1-D)) along a typical nanofiber was analyzed to be 57 nm. The chemical interactions between the CoCl(2) and PEO molecules showed that polar environment provided by CoCl(2) for the PEO molecules aided the modification of CoCl(2) molecule configuration.