A novel dual cure photopolymerizable system was developed by combining two plant-derived acrylic monomers, acrylated epoxidized soybean oil and vanillin dimethacrylate, as well as the thiol monomer pentaerythritol tetrakis (3-mercaptopropionate). Carefully selected resin composition allowed the researchers to overcome earlier stability/premature polymerization problems and to obtain stable (up to six months at 4 °C) and selectively-polymerizable resin. The resin demonstrated rapid photocuring without an induction period and reached a rigidity of 317.66 MPa, which was more than 20 times higher than that of the other vanillin-based polymers. Improved mechanical properties and thermal stability of the resulting cross-linked photopolymer were obtained compared to similar homo- and copolymers: Young’s modulus reached 4753 MPa, the compression modulus reached 1634 MPa, and the temperature of 10% weight loss was 373 °C. The developed photocurable system was successfully applied in stereolithography and characterized with femtosecond pulsed two-beam initiation threshold measurement for the first time. The polymerization threshold of the investigated polymer was determined to be controlled by the sample temperature, making the footprint of the workstations cheaper, faster, and more reliable.