In order to increase the stability in reduction with respect to polyacrylonitrile (PAN), polymethacrylonitrile (PMAN), is proposed as a matrix for plasticized polymer electrolytes, useable in lithium batteries. Highly concentrated complexes of lithium salt in PMAN homopolymer were prepared using lithium perchlorate, lithium triflate or lithium imide salts, ionic conductivities as well as spectroscopic data showing the solvating ability of PMAN. In order to prevent PMAN dissolution in usual liquid electrolytes, UV curing was carried out. Although, non-optimized, the resulting plasticized PMAN electrolytes exhibit appreciable conductivities.