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Polymeric materials have always attracted high scientific attention due to their outstanding performance and high potential applications in variety fields such as ion exchange membranes, acid catalysis and separation processes [2]. Cross- linker polymers (CP) are a class of microporous polymers that are prepared via extensive crosslinking of linear or lightly cross-linked precursor polymers. They can be usually obtained by a two- step or one- pot process, starting from several monomers [1]. The most drastic features of mentioned network polymers are their extremely high surface area and porosity, outstanding chemical stability and their desire rigidity. Polystyrenedivinylbenzene (PS-DVB) based sulfonic resins is an appropriate candidate among so-called polymers especially under the highly oxidizing environment [6]. In particular, several synthetic routs have been explored to improve the electrochemical properties of these rigid polymeric resins [5,7]. It has been experimentally supported to shifting the resin morphology from a compact heterogeneous to a highly swollen semi-gelled phase. Thus, it is preferred to incorporate the PS-DVB resins in the presence of a suitable polar organic solvent to swell the polymer framework and to generate the extensive nanometer size porosity with a high specific surface area of hundreds per gram of the polymer [3,4]. Furthermore, this facilitate the locally aligned ion-conducting channels or functional groups in the polymer complex framework and affects the electrochemical performance that have been elucidated in terms of ion exchange capacity (IEC), transport number, etc