AbstractWe investigate the effect of Rh doping in Sr₂IrO₄ using X-ray absorption spectroscopy (XAS). We observed appearance of new electron-addition states with increasing Rh concentration (x in Sr₂Ir_1−xRh_xO₄) in accordance with the concept of hole doping. The intensity of the hole-induced state is however weak, suggesting weakness of charge transfer (CT) effect and Mott insulating ground states. Also, Ir J_eff = 1/2 upper Hubbard band shifts to lower energy as x increases up to x = 0.23. Combined with optical spectroscopy, these results suggest a hybridisation-related mechanism, in which Rh doping can weaken the (Ir J_eff = 1/2)–(O 2p) orbital hybridisation in the in-planar Rh-O-Ir bond networks.