According to these studies, only a few thionolactones are available so far to prepare degradable vinyl-based copolymers, and with a peculiar reactivity that could be worthwhile to more finely tune. In this work, we thus aimed at gaining better understanding of the structure-reactivity relationship leading to efficient rROP for the thionolactone family. This will help to design in silico new structures. and ultimately, their reactivity may be thereby rationalized tuned. Reactivity ratios for the copolymerization with styrenic and acrylate derivatives closer to 1 at temperature 80-100 °C were targeted to ensure the random incorporation of the weak bonds into the polymer backbone.