GaAs/AlGaAs asymmetrical coupling double quantum wells (ACDQW) were grown with MBE with the combinative implantation method, and several areas of coupling quantum well with different implantation ion of As + and H + and different ion doses in single wafer were obtained. Without rapid thermal annealing procedure, maximum difference of transition energy of intersubbands of 100meV was found from the photoluminescence spectra measured at room temperature. During the implantation process, the energy shift caused by combinative implanation was found to be larger than that caused by ion implantation individually.