Molecular modeling showed thionated polymers to form more compact conformations, with less pronounced hydrogen bonding to water and greater desolvation of the hydrophobic surface. This work will need to be extended to different molar masses as well as to other POx and POzi to better understand the chain-length and side chain dependency of the thionation kinetics and the LCST tuning with thionation. In addition, the effect of thionation should also be studied for other water-soluble polymers with type I behavior such as poly(N-vinyl caprolactam) as well as type II behavior such as poly(N-iso-propyl acrylamide). We believe that the presented approach is adding more synthetic versatility to POx and POzi families and beyond, opening a door for further fine-tuning their physicochemical properties. Such materials could be interesting for different applications such as metal adhesives, antimicrobials or drug delivery.