The influence of the density of gap states and the band gap width of the intrinsic a-Si:H active layer on the characteristics of a-Si PIN/OLED coupling pair was analyzed by a-Si:H PIN/OLED CAD simulation model. The CAD simulation model was carried out based on a-Si PIN Hack & Shur model and OLED TCL transport model. At the same band gap width, for the intrinsic a-Si:H active layer with the higher density of gap states, the reverse current of a-Si PIN trended to be saturated at the higher reverse bias voltage. As a result, I-V curve of a-Si PIN/OLED around the turn point Vt became smoother with the increase of the density of gap states. At the same state density, the light induced current of a-Si PIN increased against the band gap width, assuming the input light had the same spectrum as AM1.5 solar light. Thus the luminance emitted from OLED increased with the decrease of the band gap width because OLED belongs to the light-emitting device controlled by current. The simulation results also showed that the influence of the state density intensified with the increase of the band gap of a-Si:H.