In this work propose an experimental strategy to explain the fast ion transport of pPEGMA /LiPF₆ electrolytes at high salt concentration with the presence of ion clusters. In this study it has demonstrate the ability to functionalize the lateral chains of pPEGMA with zwitterionic groups without altering the morphology of pPEGMA. This work show a successful functionalization of pPEGMA (pMPS8-co-PEGDMA) able to dissociate salt completely. The analysis of TG, DSC, XRD and IES show that in pPEGMA/LiPF6 at low salt concentration the ionic conductivity is coupled with the mobility of chains, the transport mechanism occur through dynamic percolation theory where the translational dynamics of the ions depends of segmental dynamics and by renewal of hopping probabilities. The monotonic increase of ionic conductions with increasing of ion clusters, is due that the ion motion is complete decoupled of relaxation chains. T_g values increase from -49 to -32 ^oC, enough to obtain a rigid polymer electrolyte in which the cation transport occur through a static ion clusters way by percolation theory. The ion conduction of the polyether pPEGMA show that it morphology reach a certain rigidity as a rubbery electrolyte when the system change to polymer in salt. Therefore pPEGMA is an ideal polymer to use in the next generation of advanced polymer electrolyte.