This paper reports on the Raman spectroscopy and the photoluminescence spectra of Nd- and W- doped BaTiO3 (BT) ceramics prepared using the molten-salt method. The samples were subjected to annealing at a temperature of 900 °C. Raman spectroscopy was carried out at room temperature on doped ceramics and pure BT. The incorporation of Nd3+ for Ba2+ in A site and W6+ for Ti4+ in B site into BT lattice was also discussed. Moreover, we controlled the frequency and damping of the main optic modes. No significant change was observed in the frequency and damping. But the only frequency of A1[TO3] mode was slightly sensitive to the Nd and W doping. This could reflect the effect of these ions on the Ti site, since this mode corresponds to a distortion of O octahedron around the central Ti ion. In addition, three different exciting laser lines were used for enlightening the Nd3+ emission effect and the contribution of the luminescence processes in the “abnormal” Raman spectra recorded for 785 nm. These abnormal Raman signals originate from a fluorescent effect corresponding to 4F5/2,3/2 →4I9/2 transitions of Ba-site Nd3+ ions. This behavior is confirmed by photoluminescence data at room temperature under 514.5 nm excitation via the presence of two peaks located at 880 nm and 909 nm corresponding to the 4F5/2,3/2 →4I9/2 transition levels, respectively, which also showed a decrease in the intensity of emission spectra following the incorporation of W6+ ions into the Ti site. The fluorescent signals were so intense that they overwhelmed the traditional Raman spectra of our compounds.