Conductivity hysteresis and room temperature ionic conductivities >10−3 S/cm were recently reported for electrolytes prepared from blends of an amphiphilic comb copolymer, poly[2,5,8,11,14-pentaoxapentadecamethylene (5-hexadecyloxy-1,3-phenylene)] (polymer I), and a linear multiblock copolymer, poly(oligotetrahydrofuran-co-dodecamethylene) (polymer II), following thermal treatment [F. Chia, Y. Zheng, J. Liu, N. Reeves, G. Ungar, P.V. Wright, Electrochim. Acta 43 (2003) 1939]. To investigate the origin of these effects, polymers I and II were synthesized in this work, and the conductivity and thermal properties of the individual polymers were investigated. AC impedance measurements were conducted on I and II doped with LiBF4 or LiClO4 during gradual heating to 110°C and slow cooling to room temperature. Significant conductivity hysteresis was seen for polymer II, and was similarly observed for poly(tetrahydrofuran) (PTHF) homopolymer at equivalent doping levels. From thermogravimetic analysis (TGA), gel permeation chromatography (GPC) and 1H NMR spectroscopy, both polymer II and PTHF were found to partially decompose to THF during heat treatment, resulting in a self-plasticizing effect on conductivity.