AbstractEmissive organic semiconductors are highly demanding for organic light‐emitting transistors (OLETs) and electrically pumped organic lasers (EPOLs). However, it remains a great challenge to obtain organic semiconductors with high carrier mobility and high photoluminescence quantum yield simultaneously. Here, a new design strategy is reported for highly emissive ambipolar and even n‐type semiconductors by introducing perfluorophenyl groups into polycyclic aromatic hydrocarbons such as perylene and anthracene. The results reveal that 3,9‐diperfluorophenyl perylene (5FDPP) exhibits the ambipolar semiconducting property with hole and electron mobilities up to 0.12 and 1.89 cm2V−1s−1, and a photoluminescence quantum yield of 55%. One of the crystal forms of5FDPAexhibits blue emission with an emission quantum yield of 52% and simultaneously shows the n‐type semiconducting property with an electron mobility up to 2.65 cm2V−1s−1, which is the highest value among the reported organic emissive n‐type semiconductors. Furthermore, crystals of5FDPPare utilized to fabricate OLETs by using Ag as source–drain electrodes. The electroluminescence is detected in the transporting channels with an external quantum efficiency (EQE) of up to 2.2%, and the current density is up to 145 kA cm−2, which are among the highest values for single‐component OLETs with symmetric electrodes.