CaGa 2 O 4 nanofibers, Ca 2 GeO 4 microfibers, CaIn 2 O 4 nanorods, and CaSnO 3 nanofibers were synthesized by using an electrospinning technique. Structures and morphologies of the as-synthesized oxides were characterized by X-ray diffraction and scanning electron microscopy, respectively. Raman and infrared spectra were also recorded and analyzed at room temperature. More significantly, nuclear site group analysis was carried out and the number of normal vibrational modes, Raman-active, and infraredactive optical phonon modes were obtained by theoretical calculation. Finally, vibrational assignments of the observed Raman peaks and infrared absorption bands were given based on the group theoretical analysis and experimental data from literature.