We present a systemic study on the structural, optical and magnetic properties of the un-doped and Mn doped ZnO thin films grown by aerosol spray pyrolysis at different deposition times. XRD profiling has shown that the structures of the prepared products are wurtzite without any evidence of second phases. Surface morphology analysis revealed that incorporation of Mn in the ZnO matrix results in the formation of “doughnut-like” structures while the corresponding un-doped ZnO showed permeable structures only at long deposition time. Optical results demonstrated that Mn-doped ZnO nanostructures exhibited both the characteristic orange Mn²⁺ ion-related emission at 595 nm and a shoulder around 667 nm, denoting that the Mn ions have successfully occupied lattice positions of Zn ions. The chemical composition and charge states of the Mn ions in the doped ZnO nanostructures analysed by the EDX and XPS, also confirmed that Mn²⁺ ions were successfully incorporated onto zinc sites in the ZnO host crystal. With the combination of defect analysis based on PL and XPS, the effect of defects on the nature and origin of ferromagnetism through EPR was investigated. These findings suggested that zinc and oxygen defects, especially zinc interstitials and singly ionized oxygen vacancies, play a crucial role in mediating ferromagnetism in the undoped ZnO.