In this work, a plant-based resin gel polymer electrolyte (GPE) was prepared by stereolithography (SLA) 3D printing. Lithium perchlorate (LiClO4) with a concentration between 0 wt.% and 25 wt.% was added into the plant-based resin to observe its influence on electrical and structural characteristics. Fourier transform infrared spectroscopy (FTIR) analysis showed shifts in the carbonyl, ester, and amine groups, proving that complexation between the polymer and LiClO4 had occurred. GPEs with a 20 wt.% LiClO4 (S20) showed the highest room temperature conductivity of 3.05 × 10−3 S cm−1 due to the highest number of free ions as determined from FTIR deconvolution. The mobility of free ions in S20 electrolytes was also the highest due to greater micropore formation, as observed via field emission scanning electron microscopy (FESEM) images. Transference number measurements suggest that ionic mobility plays a pivotal role in influencing the conductivity of S20 electrolytes. Based on this work, it can be concluded that the plant-based resin GPE with LiClO4 is suitable for future electrochemical applications.