Polymer electrolytes, which comprise a novel comb-like copolymer and an alkali metal salt, were successfully prepared and discussed using differential scanning calorimeter, Fourier transform infrared spectroscopy, nuclear magnetic resonance, atom force microscopy, and electrochemical impedance spectroscopy. The novel comb-like copolymer is capable of forming donor:acceptor type bonds with alkali metal ions. The complex system with a mixture of fumed silica or propylene carbonate was studied also. Such electrolytes possess satisfactory ambient temperature ionic conductivity (up to 10−4 Scm−1) and good mechanical strength. The Vogel–Tamman–Fulcher-like behavior of conductivity implies the coupling of the charge carriers with the segmental motion of the polymer chains.