The Poly(vinyl alcohol)/copper acetate/calcium acetate sol was prepared by sol gel route. Poly(vinyl alcohol)/copper acetate/calcium acetate composite nanofibers were synthesized by electrospinning process. These nanofibers had an average diameter of 200 nm. Calcining these fibers at 1000 degrees C produced copper oxide/calcium oxide nanofibers with average diameter of 75 nm. These fibers were characterized by Atomic Force Microscopy, Scanning Electron Microscopy, Fourier Transform Infrared spectroscopy, powder X-ray Diffraction, Ultraviolet spectroscopy, dielectric study and Second Harmonic Generation (SHG) efficiency test. Band gap energy was calculated as 4.1 eV. SHG efficiency was found to be 1.7 times than that of KDP.