Herein we introduce the all-organic triphenylsulfonium (TPS) salts cathode interfacial layers (CILs), deposited from their methanolic solution, as a new simple strategy for circumventing the use of unstable low work function metals and obtaining charge balance and high electroluminescence efficiency in polymer light-emitting diodes (PLEDs). In particular, we show that the incorporation of TPS-triflate or TPS-nonaflate at the polymer/Al interface improved substantially the luminous efficiency of the device (from 2.4 to 7.9 cd/A) and reduced the turn-on and operating voltage, whereas an up to 4-fold increase in brightness (∼11 250 cd/m(2) for TPS-triflate and ∼14 682 cd/m(2) for TPS-nonaflate compared to ∼3221 cd/m(2) for the reference device) was observed in poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-2,1',3-thiadiazole)] (F8BT)-based PLEDs. This was mainly attributed to the favorable decrease of the electron injection barrier, as derived from the open-circuit voltage (Voc) measurements, which was also assisted by the conduction of electrons through the triphenylsulfonium salt sites. Density functional theory calculations indicated that the total energy of the anionic (reduced) form of the salt, that is, upon placing an electron to its lowest unoccupied molecular orbital, is lower than its neutral state, rendering the TPS-salts stable upon electron transfer in the solid state. Finally, the morphology optimization of the TPS-salt interlayer through controlling the processing parameters was found to be critical for achieving efficient electron injection and transport at the respective interfaces.