Wurtzite ZnO/MgO superlattices were successfully grown on Si(001) substrates at 750℃ using radio-frequency reactive magnetron sputtering method. X-ray reflection and diffraction, electronic probe and photoluminescence analysis were used to characterize the multiple quantum wells (MQWs). The results showed the periodic layer thickness of the MQWs to be 1.85 to 22.3 nm. The blueshift induced by quantum confinement was observed. Least square fitting method was used to deduce the zero phonon energy of the exciton from the room-temperature photoluminescence. It was found that the MgO barrier layers has a much larger offset than ZnMgO. The fluctuation of periodic layer thickness of the MQWs was suggested to be a possible reason causing the photoluminescence spectrum broadening.