Dilute magnetic semiconductors such as transitionmetal-doped ZnO are potential candidates for spintronic applications. Transition metals such as Mn, Fe, and Cu when doped in ZnO enable spin magnetic properties to conventional semiconductors. Although several techniques such as wet chemical and vapor deposition methods are employed to achieve homogeneous doping in ZnO, these methods have limits pertaining to solubility levels of dopant ion, morphology, competition between intrinsic and extrinsic defects and localization of the defect species. This manuscript is an addition to the vast knowledge of methods and protocols that present the synthesis of transition-metal-doped ZnO. In this report, manganese-doped ZnO is synthesized via a microwave-assisted hydrolysis technique. The defect structure of Mn-doped ZnO wires is investigated via electron paramagnetic resonance and photoluminescence techniques. The analysis indicates that Mn2+ substitutes the Zn ion and dominates the intrinsic defect species in ZnO.