Blue emitters with outstanding luminous performance must be synthesized for full-color organic light-emitting diode displays. The hybridized local and charge transfer (HLCT) is a remarkable excited state that combines the local and CT state to ensure a significant fluorescence quantum yield. The ambition of this study is to implement a subtle interpretation of photophysical and electroluminescence (EL) properties. To understand more about the geometry and orientations, the density functional theories were studied. Herein, we present a hybrid donor-π-acceptor blue-emitting fluorophore with a twisted geometry, in which triphenylamine (TPA) acts as a donor, 9,9 diethylfluorene acts as a spacer, and benzilimidazole acts as an acceptor. The EL spectra of the device are very similar to spectra of photoluminescence in the solution phase. Among all, the best performing 15 wt % MCFBI-fl-TPA-based OLED device illustrates a maximum luminance of 3290 cd/m2. The device shows 8.2 lm W-1 of power efficiency, 7.9 cd A-1 of current efficiency, and 3.5% of high external quantum efficiency with (0.20, 0.23) of CIE coordinates of the device emitting blue color. © 2023 American Chemical Society.