The conductivity performance of commercial available room-temperature ionic liquids (RTILs) has been evaluated from room conditions up to 200 degrees C as a function of relative humidity for their potential application in high temperature PEMs. In particular, ammonium and imidazolium based ionic liquids with different counterions and substituents have been investigated. On the basis of conductivity performance, the best RTILs have been selected for the preparation of all solid state ion conductive films by bulk photo-assisted radical polymerization. The goodness of the UV photopolymerization of the respective monomeric ionic liquids (MILs) with vinyl functionality as a function of divinylbenzene cross-linker content has been evaluated by TGA and PTIR analyses. Poly-ionic liquid (PIL) films have been successfully accomplished for polymerized H-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide upon exposure to 365 nm LTV lamp with an intensity of 2.4 mW/cm(2) for 15 min. Conductivity values above 1.1 S cm(-1) at 200 degrees C have been registered for pure poly[1-(3H-imidazolium)ethylenel bis(trifluoromethanesulfonyl)imide. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.