We report on the structural and electrical properties of Mn-doped ZnO/Al(2)O(3) nanostructures produced by the pulsed laser deposition technique. Grazing incidence small angle x-ray scattering (GISAXS) and Rutherford backscattering spectrometry revealed the multilayered structure in as-deposited samples. Annealing of the nanostructures was shown to promote the formation of nanocrystals embedded in the Al(2)O(3) matrix, as was evidenced by GISAXS and high resolution transmission microscopy. Particle-induced x-ray emission analysis showed a doping of 8 at.% Mn in ZnO. Grazing incidence x-ray diffraction and Raman spectroscopy demonstrated that the nanocrystals have the pure wurtzite ZnMnO crystalline phase. Resonant Raman scattering displayed an increase of intensity of the 1LO mode as well as broadening of the 2LO mode related to the size effect. Capacitance-voltage measurements showed carrier retention with a voltage shift higher than those reported for similar systems.