Mn-doped ZnO samples with 5%, 20% and 40% nominal Mn concentrations were prepared in the presence of ethyl acetoacetate under solvothermal conditions. UV absorption spectroscopic analysis discloses that chemical modification was achieved by reaction of Zn or Mn precursor with ethyl acetoacetate in ethanol medium. XRD and HRTEM characterizations indicate that ZnMnO 3 impurity phase was formed in the 20% and 40% Mn-doped ZnO samples while no secondary phase was present in the 5% Mn-doped sample. The 5% Mn-doped sample consists of spheroid-like particles with size of 10–50 nm and has a real Mn concentration of 3.2%. Ferromagnetism and paramagnetism coexist in the 5% Mn-doped ZnO sample at room-temperature, which may arise from ferromagnetic exchange interaction as well as small secondary phases. The 20% and 40% Mn-doped samples show large paramagnetic effects at room temperature. Small paramagnetic secondary phases and clustering of Mn are probably responsible for this.