Fluoro substitution of organic semiconductors is an effective way to improve some related performance of the materials, such as the carrier mobility in organic photovoltaics (OPVs) and organic field-effect transistors (OFETs) applications. However, the influence of fluoro substitution for fluorophores in organic light-emitting diodes (OLEDs) applications is rarely reported. Here, with fluorinated electron-deficient 2,1,3-benzothiadiazole (BT) unit as the acceptor and triphenylamine (TPA) as the donor, we construct two new D-A-type fluorophores DTPA-fBT and DTPA-ffBT. Theoretical calculations and experimental results reveal that the lowest excited states (S1) of the materials are characterized by hybridized local and charge-transfer (HLCT) properties, in which the fluorine substitution will increase the proportion of the charge-transfer (CT) component. Due to the introduction of fluoro substitution, multiple fluorine hydrogen bonds are formed, which endow the molecules with more rigid conformation, leading to lower non-radiative rates and higher photoluminescence quantum yield (PLQY) in solution and doped film, as well as improved thermal stability in the solid state. As a result, the two fluorinated DTPA-ffBT demonstrate significantly improved performance in OLEDs with a maximum external quantum efficiency (EQE) of 7.25% (5.90% for fluorine-free counterpart) and very low-efficiency roll-off (roll-off <7% at 10,000 cd m-2).