Photo-cured 3D architectures are successfully printed using the designed waterborne polyurethane-acrylate (WPUA) formulation. A WPUA series is synthesized in the presence of polycaprolactone diol (PCL) and 4,4′-methylene dicyclohexyl diisocyanate (H12MDI) as the soft segment part, dimethylolbutanoic acid (DMBA) as the emulsifier, and triethylamine (TEA) as the neutralizer, as a function of prepolymer molecular weight. The compatibility of WPUA and the photo-activating acryl monomer is as a key factor to guarantee the high resolution of 3D digital light processing (DLP) printing. The optimized blending formulations are tuned by using triacrylate monomers instead of diacrylate derivatives. For the high-accuracy and fine features of 3D DLP printing, WPUA are designed to be a suitable molecular structure for a 385 nm wavelength source, and the target viscosity is achieved in the range from 150 to 250 Cp. Photo-cured 3D architectures based on WPUA exhibit good flexural strength and high resolution.