Abstract This work investigates the suppression of n-channel and the switch of transfer characteristics (from n-type to ambipolar) by illumination in n-type pentacene-based organic field-effect transistors (OFETs). The illumination outcomes differently on the output characteristics of OFETs, which markedly decreases the magnitude of drain current (n-channel) and shifts the turn-on voltage to a higher positive bias in the n-type regime, but induces the formation of p-channel in the p-type regime. We attribute that the trapped negative charges in the device as induced by illumination electrostatically shield the effective electrical field applied to the gate with source/drain electrodes and modulate the device performance. The result of quasi-static capacitance–voltage measurement agrees well with the modulations of the transfer characteristics for n-type OFETs by illumination. In addition, the de-trapping of charges recovers the n-type only output characteristics of pentacene-based OFETs. This study highlights the unique photo responses of n-type pentacene-based OFETs to the development of phototransistors of distinct output characteristics operated in n- and p-type regime.