With the aim to generate non-conventional biobased solid electrolytes, we exploit the synergistic interactions between galactomannan chains and hydrophilic imidazolium ionic liquids (IL). More particularly, we selected guar gum as galactomannan related to - its abundance, - non-toxicity, - its peculiar structure, - its high thermal stability and the commercial availability of very high molecular weights. We recently demonstrated that such guar/IL association leads to solid-like gels with relevant rheological, thermomechanical and conductive properties [1,2]. Based on these advanced research, we are now focusing on the development of ternary blends presenting a higher degree of sophistication by incorporating additional reinforcing building-blocks, such as imidazolium-based poly(ionic liquid) (PIL), in view of generating biohybrid materials with enhanced properties. We synthesized a series of PIL by RAFT polymerization and we particularly showed the excellent control of the polymerization [3]. PIL are promising synthetic polymers which combine the unique attributes of ionic liquids (thermal and chemical stability, non-inflammability, non-volatility and conductivity) with the ones of polymers in terms of mechanical reinforcement, and dimensional stability. Structure/properties relationships of the resulting multicomponent systems were in-depth investigated. The rheological, thermal and conductive properties were methodically studied and correlated with the morphology of the biohybrids by means of synchrotron scattering measurements [4]. The concept presented herein, based on biosourced polymer-containing multi-component systems represents a promising route for the design of advanced conductive materials. [1] C. Lacroix, E. Sultan, E. Fleury, A. Charlot, Polymer Chemistry, 2012, 3, 538. [2] L. Verger, S. Corre, R. Poirot, G. Quintard, E. Fleury, A. Charlot, Carbohydr. Polym., 2014,10,932. [3] B. Zhang, E. Fleury, A. Charlot, J. Bernard, ACS Macro Letters, 2015, 4, 1008. [4] B. Zhang et al., submitted to J. Mater . Chem. A.