Triphenylsulfonium salts addition in the emitting layer of polymer light emitting diodes (PLEDs) has been shown to be beneficial for charge injection and transport due to both ionic effects and π-conjugation in the phenyl rings of the cation. In some cases the emission profile can be also modified through an electroplex formation. Herein we investigate the effect of four TPS-salts with different counter anions on the overall PLED performance upon blending each salt with the conjugated polymer poly[2-(6-cyano-6-methyl-heptyloxy)-1,4-phenylene] (CN-PPP). In particular, three perfluoroalkanesulfonate organic anions of increasing size (triflate, nonaflate, PFOS) and a perfluorinated inorganic anion (SbF6) are compared. It is shown that the anion size affects primarily the turn-on and operational voltage, whereas its chemical nature is crucial for achieving high luminance values. The counteranion exerts also a direct impact on the dispersion properties of the salt in the polymer matrix, and thus, the film morphology, which in turn influences the emission colour and efficiency of an electroplex that is proposed to be formed at the sulfonium salt/polymer interfaces in the bulk. This study highlights the importance of properly selecting the counterions of the salts added in the emitting layer of PLEDs, which, in addition to their various functionalities, significantly influence device performance.