Single and fast ion transport in all-solid-state-flexible-electrolyte systems is desired for energy devices. The commercially used polymer electrolytes consist of liquid component to achieve the requiredelectrochemical properties and they also suffer from slow and poor cation transfer.Thepolymer-in-salt-electrolytes (PISEs) are supposed to lead to single and fast ion transport, unfortunately polymer hosts and salts,which can lead to successful synthesisof PISE with targeted minimum conductivity (10-4 S/cm) with suitable morphology is still to be identified.All efforts resulted either in poor electrochemical properties and/or poor morphology because of recrystallization of salt. Here novel PISEsare discussedwhich have high conductivity (0.1 S/cm) and small ion relaxation time (10 μ sec) with wide electrochemical-stability-window (> 2.5V). Since in PISEs the ion transport is decoupled from polymer segmental motion and it takes place through ion cluster, hence it is of immense importance to understand how the host matrix affects electrochemical properties of PISEs, hence three different starches (potato starch, corn starch and arrowroot starch) have been selected keeping all other constituent chemical and synthesis process same. Signature effects of host starches are observed and discussed.