Asymmetric (CuGaO2/ZnO/ZnMgO) and symmetric (ZnMgO/ZnO/ZnMgO) multiple quantum well (MQW) structures were successfully fabricated using pulsed laser deposition (PLD) and their comparison were made. Efficient room temperature photoluminescent (PL) emission was observed from these MQWs and temperature dependent luminescence of asymmetric and symmetric MQWs can be explained using the existing theories. A systematic blue shift was observed in both MQWs with decrease in the confinement layer thickness which could be attributed to the quantum confinement effects. The PL emission from asymmetric and symmetric MQW structures were blue shifted compared to 150 nm thick ZnO thin film grown by PLD due to quantum confinement effects.