Organic Electrochemical Transistors (OECTs) were fabricated with two kinds of highly conducting polymer electrolytes, one with cations of small dimensions (Li+) and the other with cations of large dimensions (1-ethyl-3-methylimidazolium, EMI+). All OECTs exhibit transconductance values in the millisiemens range. Those with the larger EMI+ cations reach higher transconductance values and the saturated region of their I(V) characteristics extends to drain negative voltages of the order of −2 V without breakdown. These OECTs aim at potential applications for which it is relevant to use a solid polymer electrolyte instead of an aqueous electrolyte, namely, for integration in complex devices or in sensors and transducers where the electrolyte film may act as a membrane to prevent direct contact of the active material (PEDOT:PSS) with the biological media. The choice of electrolytes with cations of disparate sizes aims at assessing the nature (Faradaic or capacitive) of the processes occurring at the electrolyte/channel interface. The results obtained are consistent with a Faradaic-based operation mechanism.