Energy storage is of great importance in our modern society and further research is required to improve its efficiency and for it to be better for the environment. Thus, plasticized solid biopolymer electrolytes (SBEs) based on carboxymethyl cellulose were prepared for a solid-state hydrogen energy storage application. The transport properties of the SBEs were determined using FTIR deconvolution techniques at the wavenumber region of 1505 to 1355 cm−1. It was found that the conductivity of SBEs were influenced mainly by ions mobility, μ and diffusion coefficient, D. A solid-state hydrogen ionic cell (SSHC) was then fabricated from the best performing SBE and evaluated. A rechargeable SSHC with the configuration of Zn + ZnSO4·7H2O/SBE/MnO2, produced a maximum open circuit potential of 1.1 V at ambient temperature and showed good rechargeability for 10 cycles. Our findings suggest for a novel practical application of the present bio-electrolyte in the fabrication of solid-state hydrogen ionic cells.