The synthesis procedure of rapeseed oil acrylayes and epoxides is reported. The received resins can be blended with different biobased reactive diluents to prepare stable formulations. While the addition of low-content nanocellulose additives can provide a tool to control the viscosity of the resins, which are requested to be printed by light processing with a vat or syrenge 3D printers. The photorehology was used to characterize the viscosity changes during phtotocuring processing. The spatial cell-type structure of TENG devices has been printed for energy harvesting measurements. The thermal, mechanical, and thermomechanical performance of the developed and printed biopolymers was tested. The elastomeric performance and ductility of the biopolymers depend on the chosen chain extension by reactive diluents. It strongly impacts surface-charged generation and final energy harvesting performance. The accelerated weathering aging of the printed biopolymer structures showed a strong dependence on the resin formulation, while the biodegradation of the thermoset bioacrylates was evaluated, and the circularity of the approach used was also evaluated to recover the raw components. The TENG device performance can be compared with the fossil polymer analogs.