Nano-sized ZnO doped with transition metals is one of the most promising candidates in the field of diluted magnetic semiconductors unifying ferromagnetic and semiconductor properties. Promising is the exploitation of the magnetic spin of the electron and by that the application in spintronics. Asthe mechanism of spin coupling is still controversial, insight into the coexistence and interaction of intrinsic and extrinsic effects is vital for further technological progress. We report on the synthesis of a set of nanosized Zn1-xMnxO samples with a nominal concentration of x = 0.000005–0.03 and structural (XRD, TEM, and AFM), as well as electronic (PL, UV–Vis, FTIR, and EPR) investigations. In this contribution, possible interaction effects were summarized in terms of Mn doping and size. PL quenching after doping was also discussed as another aspect for the interrelations of the defects.