This paper describes studies of the interface between lithium electrodes and solid electrolyte systems using in situ FTIR spectroscopy in a single internal reflectance mode. In this method, the masking effect of the electrolyte matrix components is largely avoided. We studied gel electrolytes based on polyvinylidene difluoride-hexafluoropropylene with cyclic alkyl carbonates as plasticizers, suitable for ambient temperatures, and a solvent free polymer, derivatives of polyethylene oxide (PEO) with a branched structure: polyethyleneoxide-2-(2-methoxyethoxy)ethyl glycidyl ether at elevated temperatures. We found that the surface chemistry of Li electrodes in contact with the gel matrixes is dominated by alkyl carbonate solvent reduction to ROCO 2Li surface species. In the case of the PEO-based polymer, the surface reactions of Li electrodes are dominated by salt and trace water reduction. The polymer itself seems to be stable with lithium even at 60°C.