For the first time, the concept of fluorophilicity f(i) is adapted to the development of a novel solid polymer electrolyte (SPE) by computationally evaluating a new class of lithium salts, the perfluoroalkylated pyrazolides. An SPE consisting solely of poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) and different concentrations of highly-fluorous lithium [5-(perfluorobutyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl] trifluoroborate (LiPFAPB14) is reported. Membranes with a salt concentration up to 80 wt.% are prepared and are investigated by 3D laser scanning confocal microscopy, scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) concerning the correlation between the LiPFAPB14 salt concentrations with the miscibility in PVDF-HFP. Membrane performances as SPE are evaluated by impedance spectroscopy revealing ionic conductivities of 1.4 x 10(-4) S cm(-1) at 90 degrees C with 80 wt.% LiPFAPB14. (C) 2016 Elsevier B.V. All rights reserved.