A novel 3D printable gel polymer electrolyte (GPE) based on N,N-dimethylacrylamide (DMAAm) and polyvinylidene fluoride (PVDF) are prepared and characterized. 3D printing of DMAAm containing PVDF and ethylene glycol (EG) based liquid electrolyte yields chemically cross-linked PVDF/DMAAm gel polymer electrolyte. A customized 3D gel printer named “Soft and Wet Intelligent Matter-Easy Realizer” (SWIM-ER) is used to fabricate PVDF/DMAAm based GPE via optical method of stereo-lithography. This gel polymer electrolyte exhibits a good ionic conductivity and mechanical properties. Meanwhile, the gel polymer electrolyte shows very good thermal stability.