The use of polyethylene glycol dimethacrylate (PEG-DMA) is extensive in tissue engineering due to its mechanical properties, lack of immunogenicity, recognized cytocompatibility, and ease of synthesis. In our study, PEG-DMA of 550 and 750 Da number average molecular weight polymer-based 3D printable solutions were prepared in a double photo-initiator system including riboflavin (Rb)/triethanolamine (TEA) and water-soluble diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (wsTPO). The 3D printable ink solutions and their consecutive hydrogels were investigated by rheological parameters, compressive and tensile mechanical properties, water swelling, contact angle measurement, and FTIR analysis. The results demonstrated that both PEG-DMA (Mn: 550 and 750) hydrogel systems were successfully printed using Rb/TEA and wsTPO photo-initiator system with an SLA 3D printer, making it an important form of hydrophilic polymer for biomedical applications, as well as in the field of dentistry such as surface modification, bioconjugation, drug administration, tissue engineering, and periodontal regenerative surgery. These properties of the 3D-printed hydrogels make these promising candidates for these applications in the near future.