Poly(3,4-ethylenedioxythiophene):poly(styrenesulphonic acid) (PEDOT:PSS) is commonly used as an anode in polymer light-emitting diodes (PLED). We have studied the effect of the pH and Na+ ion concentration of the aqueous PEDOT:PSS dispersion on the bulk and surface properties of spincoated films by various techniques, including UV-vis-NIR optical absorbance spectrometry, Raman spectroscopy, X-ray Photoelectron Spectroscopy (XPS) and Ultraviolet Photoemission Spectroscopy (UPS). A pH increase by addition of NaOH modifies the PEDOT : PSS properties in a similar way as electrochemical dedoping: the IR absorbance decreases, the Raman peaks shift, sharpen and increase in intensity, and the work function decreases. Consequently, a barrier for hole injection is introduced for several classes of light-emitting polymers. We argue that the mechanism of the pH-effect is different from electrochemical dedoping, and originates from a change in the relative stability of polarons and bipolarons on the doped thiophene. The changes in the electronic properties of PEDOT:PSS point to the determining role of the counter-ion in the stabilisation of oxidised thiophene units. Polymer LEDs comprising Na+-rich, proton poor PEDOT:PSS can show lower lifetime and efficiency than the corresponding Na+-free, proton-rich devices. For light emitting polymers which suffer from the addition of sodium to the hole injecting PEDOT:PSS, the decreased lifetime hints at hole injection as limiting factor in the degradation of these PLEDs.