Electrical conductivity, differential scanning calorimetry (DSC) and Li-7 nuclear magnetic resonance (NMR) studies have been carried out on liquid electrolytes such as ethylene carbonate:propylene carbonate (EC:PC) and EC:dimethyl carbonate (DMC) containing LiPF6 (and LiCF3SO3 for NMR) and films plasticized using the same liquid electrolytes. The films are based on poly(vinylidene fluoride) (PVdF) copolymerized with hexafluoropropylene and contain fumed silica. All measurements were carried out at atmospheric pressure from room temperature to about -150 degrees C and the electrical conductivity studies were performed at room temperature at pressures up to 0.3 Cpa. The liquids and hybrid electrolytes are similar in that the electrical conductivity of the EC:PC-based substances exhibits Vogel-Tammann-Fulcher (VTF) behaviour while that for the EC:DMC-based substances does not. Part of the deviation from VTF behaviour for the EC:DMC-based materials is attributed to crystallization. Further, the glass transition temperatures as determined from NMR, DSC and electrical conductivity measurements are about the same for the liquids and hybrid electrolytes. However, substantial differences are found. The electrical conductivity of the hybrid electrolytes at room temperature is lower than expected and, more importantly, the relative change of conductivity with pressure is larger than for the liquids. In addition, above the glass transition temperature, the NMR T-1 values are smaller and the NMR linewidths are larger for the hybrid electrolytes than for the liquids while at both low and high temperature the NMR linewidths are larger. Consequently, it is concluded that significant solid matrix-lithium ion interactions take place.