Inserting intermediate layers in transition metal dichalcogenide heterostructures (TMD HSs) has become an efficient approach to modulating interlayer charge transfer rates. However, it could not only modify the distance of charge transfer but also potentially alter the interlayer coupling strength within HSs, which would profoundly influence the charge transfer rate in the opposite direction. Here, to gain insight into the dual roles of inserted intermediate layers in multilayer TMD HSs, MoS