Ba(Mn1/3Nb2/3)O-3 ceramics were synthesized by the microwave-hydrothermal process. Crystalline, single-phase, needle-like materials were obtained with high anisotropy and aspect ratio. Large crystals could be prepared from a direct combination of nanosized crystals under microwaves through an oriented attachment mechanism, Infrared and Raman spectroscopies showed perfect agreement with group-theoretical approaches for a trigonal, P (3) over bar ml structure. Franck-Condon modes were identified in Raman scattering experiments conducted in different wavelengths, laser powers, and temperatures. The results showed that the Mn ions exhibit a particular role in the lattice dynamics in complex perovskites.