In this paper we studied the spectro-mechanical properties of polymer gel electrolytes and blends by means of shear rheology. These electrolytes were obtained by immobilizing EC/PC/LiClO4 solutions in a polymeric matrix of PEO, PAN and PMMA, respectively. Two structural and thermoreversible transitions, a strong-to-weak gel and a gel-to-sol, were revealed and discussed. Moreover, PMMA-PVdF blends have been studied as a function of the different polymeric ratios in order to obtain the best compromise between ionic conduction and mechanical properties. Interesting mechanical properties were observed at some intermediate blend compositions.