Polymers with phosphorus in the main chain with intrinsic disordered framework for lithium-ion conductivity were synthesized. Conductivity of one of the solid polymer electrolytes prepared from those polymers with 40 wt% of LiTFSI was 8.9 x 10(-4) S cm(-1) at 30 degrees C and 5.3 x 10(-3) S cm(-1) at 80 degrees C. The impressive conductivity is explained by the availability of high conduction pathways provided by frozen chain disorder. (C) 2015 Published by Elsevier Ltd.