The synthetic freedom to operate is highly dependent on the final application. In polymer science, scalable reactions, simple purification, and the ideal use of renewable and relevant precursors are relied on. This work explores the ring-opening of oxiranes with acrylic acid (AA) toward β-hydroxy acrylates; great care is given to the synthetic aspects of the transformation. In addition to its simplicity, and high yield (isolated yield 68%–87%), the methodology is scalable, atom-economic, and associated with simple purification. Dependent on the initial oxirane, access to a wide range of polymeric properties with a modulus ranging from 0.3 to 630 MPa, strength from 0.3 to 19 MPa, and elongation-at-break from 3% to 170% is demonstrated. All four polymers explored are thermally stable above 250 °C and highly transparent. This work emphasizes the potential of AA as a nucleophile for direct access to monomers for a wide range of polymer applications.