In this work, we prepared ZnO, ZnAl2O4, and ZnAl mixed oxides with different metal molar ratios and applied them for synthesizing glycerol carbonate (GC) from glycerol and urea. The reaction routes related to the Zn species over the ZnAl mixed oxides were investigated. The ZnAl mixed oxides were found to consist of two Zn crystalline phases: ZnO and ZnAl2O4. From the reaction results, the ZnAl mixed oxides showed much higher glycerol conversion and GC yield than the ZnO and ZnAl2O4. During the reaction, the dissolution of the Zn species from the ZnO phase over the ZnAl mixed oxides was observed while the ZnAl2O4 phase remained insoluble. The ZnO phase provided a homogeneous reaction route via the dissolved Zn species, resulting in the formation of a Zn complex containing the isocyanate (NCO) and zinc glycerolate. In contrast, the insoluble ZnAl2O4 phase was responsible for not only a heterogeneous reaction route, but also adsorption of the Zn NCO complex on the catalyst. We proposed that the adsorbed Zn NCO complex could play a role as an active site for an additional heterogeneous reaction route. Therefore, the ZnAl mixed oxides exhibited high GC yields through the dual catalysis routes: the homogeneous reaction route over the ZnO phase and the heterogeneous reaction route over the ZnAl2O4 phase.