Optical properties of ZnO doped with Mn and V were studied. Zn(Mn)O layers were grown by peroxide MBE, and Zn(V)O was prepared by high-dose ion implantation of bulk ZnO prepared by hydrothermal technique. The Zn(Mn)O layers containing up to 50% of Mn were characterized by high-resolution x-ray diffraction, photoluminescence, and optical absorption. A blue shift of the band edge revealed from optical absorption measurements points to the incorporation of at least a part of Mn atoms on the lattice sites. An increase in the Zn(Mn)O band gap and an enhancement of the broad below band gap absorption associated with Mn ions were observed with increasing Mn composition. Correlating structural and optical transmission data, we suggest that the band edge of Zn(Mn)O rises linearly with the amount of Mn ions substituting Zn on the lattice sites. Photoluminescence of ZnO moderately doped with Mn shows several emission lines (the strongest ones are located at 3.34 and 3.36 eV). Surprisingly, no shift in the near-band-edge emission (3.36 eV) was detected in the photoluminescence data. Photoluminescence excitation studies revealed that the near-band-edge peak and the peak centered around 3.34 eV have different origin. Most probably, the second line is due to Mn intracenter transitions. Photoluminescence studies of ZnO bulk samples implanted with V+ have revealed that thermal annealing at 800 °C restores to a large extent the optical quality of the material. A new emission line centered at 3.307 eV has been found in the photoluminescence spectrum of the highly conductive samples implanted with a V dose of 1 × 1016 cm-2.