The scientific and technological developments in the field of materials science and engineering have taken multiple strides in the social growth of mankind in the past century. It is the result of these innovations that in the world of today, materials extensively dominate several sectors like structural engineering, transportation engineering, aerospace engineering, communication engineering, electrochemical and health of biomedical engineering. Surrounded by the vast array of materials, ionic materials in the past few decades have added a new dimension for the growth of science and technology termed as Polymer Electrolytes (PEs). It is the result of these advances that in the world of today, polymer electrolytes are dominating in ionic materials. Continuous efforts have been devoted to develop newer ion conducting materials and their distinctive properties have brought to vanguard their applications for electrochemical devices such as electrochromic windows, supercapacitors, high energy density batteries, micro/nano electrochemical sensors etc. but the ion conducting polymers called polymer electrolytes are receiving remarkable attention because of their immense potential applications. Although, liquid electrolytes (LEs) show excellent electrochemical performance but suffer from limitations resulting them to be conveniently replaced with PEs such as low operating temperature range, liquid oozing, internal short circuiting and the encapsulation of a liquid is difficult which restricts the shape and size of electrochemical devices. On the other hand, solid polymer electrolytes (SPEs) are stable at higher temperatures but they are limited by their conformality and have relatively lower conductivity. Currently, there is no such electrolyte that meets all the qualifications but gel polymer electrolytes (GPEs) are attractive candidates for such a system. The fundamentals of GPEs with respect to conductivity and cation solvation are the important parameters for the development of various electrochemical devices.