The pure-bromide quasi-2D perovskite has shown advantages in fabrication of blue perovskite light-emitting diodes (PeLEDs) due to its relatively good color stability and capability of moisture resistance. However, the performances of efficiency and luminance of pure-bromide quasi-2D PeLEDs with true-blue (470 nm−480 nm) emission are still inferior. Here, we show a interfacial modification strategy of involving perfluorooctanoic acid (PFOA) to a hole transport layer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), to improve the performances of the true-blue PeLEDs. The PFOA regulates the molecular conformation of PEDOT:PSS, forming ordered PEDOT domains that improves the carrier transport and a more favorable band alignment with the perovskite emissive layers. The achieved true-blue PeLEDs show peak EQE of 6.86 % and maximum luminance of 854.10 cd/m2 at wavelength of 478 nm, which are the record values for the pure-bromide quasi-2D PeLEDs in true-blue region. Moreover, owing to the hydrophobic fluorine-carbon (C-F) chains of PFOA, we successfully fabricate the blue PeLEDs in air condition without inert gas protection. This work paves the way for commercial applications in next-generation display technologies.