Highly hierarchical barlike and flowerlike MnWO 4 microcrystals have been synthesized for the first time by a hydrothermal method, where ethanolamine (EA) and cetyltrimethylamonnium bromide (CTAB) play important roles in directing growth and self-assembly of these structures. The possible formation process has been proposed. In addition, platelike nanosized MnWO 4 was also synthesized by annealing of a precursor obtained by coprecipitation method. The obtained samples were characterized by XRD, SEM, TEM, Raman and IR methods. Raman spectra showed relatively weak dependence on particle size and morphology of the particles. In contrast to this behavior, IR-active bands showed pronounced shifts and changes in relative intensities on particle size and the morphology. Origin of this behavior is discussed.