The effect of processing history and morphology is of particular importance for lithium-ion electrolytes for achieving higher ionic conductivities. In this study, single ion conducting poly (4-lithium styrene sulfonic acid) was synthesized by neutralization reaction from polystyrene sulfonic acid, and the effect of morphology and processing method was studied by comparing pelletized, electrospun and gel samples. The PSSLi gels displayed best ionic conductivity, while the pelletized samples showed the worst ionic conductivity. Although electrospinning led to a free standing electrolyte, the lower amount of solvent phase led to lower ionic conductivity when compared to the PSSLi gel. The ionic conductivity at room temperature improved from 6.6 x 10(-5) S/cm to 1.4 x 10(-3) S/cm by optimizing the processing methodology and the lithium ion concentration. The results show that PSSLi based single ion conducting lithium (SICL) gels are a promising candidate for lithium ion battery application. (C) 2016 Elsevier Ltd. All rights reserved.