A systematic study was carried out to determine the effect of the composition and annealing atmosphere (air and N2) on the structural, optical and magnetic properties of pure, doped and co-doped ZnO [Zn(1-y)(CoV)yO] nanocrystalline powders and films. The (Co+V) doping level, ‘y’, was fixed at 2 at% with variable individual concentrations of Co and V species. Powders and films were synthesized via a sol-gel approach where the films were grown on silicon (100) substrates. X-ray diffractometry verified the formation of the ZnO host structure after annealing of the precursor phases. The variation of the average crystallite size of Co-V (2 at.%) ZnO powders annealed in air at 500°C were negligible and averaged 33 nm. Photoluminescence (PL) measurements of powder corroborated the formation of high-quality ZnO host structure, as well as in films annealed in air. In turn, XRD and PL measurements confirmed an enhanced crystallinity of the ZnO host, with an average crystallite size of 41 nm, for films annealed at 500°C under a N2 atmosphere. M-H measurements evidenced a ferromagnetic behavior at room temperature in powders and films that was dependent on the type and amount of the dopant species.