Polyurethanes (PUs) are one of the most versatile classes of polymers, and their demand as high-performance industrial materials continues to grow. In this work, new polyurethane acrylates were prepared from diglycidyl ether bisphenol A (DGEBA), substituted acrylic acids, and 4,4'-diphenylmethane diisocyanate using a two-step polymerization methodology. The polymers were characterized by infrared spectroscopy, H-1 NMR spectroscopy, gel permeation chromatography, thermogravimetry, and X-ray diffraction. The influence of the structure of the acrylic acid on the reactivity with DGEBA was investigated. Density functional theory and canonical structures supported the reactivity order of the substituted acrylic acids toward DGEBA in both the gas and solution phases. All of the polyurethane acrylates investigated were found to have a high thermal stability.