Characteristic 4f photoluminescence of Eu3+ doped into ZnO was first observed on the red band luminescence. The intensity and fine structures of the Eu3+ luminescence and their temperature dependence are strongly influenced by the doping conditions. In particular, for the increase of the Eu3+ luminescence intensity Li codoping is not effective but stoichiometric control of Zn and O is essential. Moreover, the observed red band luminescence can be considered to be due to excess oxygen.