Amorphous polyesters based on rigid alicyclic monomers are increasingly seen as promising candidates to substitute polycarbonates in demanding applications. It shows different precise calculation approaches in modern coatings development, ways to formulate polyester and alkyd resins in experimental designs and how to vary them systematically. Tg values ranged from 75 to 103 °C, depending on the microstructure and molecular weights. In addition, isosorbide was introduced as a bio-based comonomer, producing amorphous copolyesters with Tg values between 81 and 97 °C. The results underline the potential of alicyclic polyols to deliver sustainable, high-performance polyester materials.