A three-pair AlGaN/GaN multiple quantum well (MQW) structure with superlattices (SLs) was grown on c-plane sapphire using metal organic chemical vapor deposition (MOCVD) system. The AlGaN barrier and GaN well of the MQW structure were grown by atomic layer deposition (ALD) and conventional growth, respectively. The HRTEM and HRXRD results show the grown structure has shape interface between SLs layers and QWs with good periodicity. The AFM and SEM data show smooth surface morphology with low RMS value and low defect density. The CL measurements also indicate uniform luminescence pattern at room temperature. The AlGaN/GaN MQW with AlN/GaN SLs structure grown by ALD could be used to improve the surface morphology by effectively suppress the threading dislocation.