Polyhydroxyurethanes (PHUs) are phosgene and isocyanate-free polyurethanes (PUs) that are foreseen as a promising alternative to conventional polyurethanes (PUs), when European and North American directives will restrict the use of allergenic and carcinogenic isocyanates. They are usually obtained through the polyaddition reaction of diamines onto bis(5-membered cyclic carbonate)s (bis-5CC), resulting in the formation of urethane linkages and hydroxyl groups (OH) (scheme 1). The success of PHUs is largely related to the rapid development of sustainable procedures for the synthesis of 5CC precursors such as the CO2/epoxide coupling chemistry or the carbonatation of biosourced 1,2-diols. However, 5CC aminolysis comes with several drawbacks including (i) slow kinetics and extensive side reactions that hinder high polymerization degree and (ii) a lack of regio-and stereo-control resulting in poorly defined polymers. Many catalysts have already been proposed to accelerate the polymerization kinetics, including N-bases, metal salts and thiourea compounds. While they accelerate the reaction, they currently do not solve the regio-and stereo-regularity issues. Yet, regularity in the arrangement of polymer backbones neighboring units is of paramount importance, as it is critical to their bulk performances. It includes their thermomechanical properties but also, when it applies, their optoelectrical behavior or their biodegradability. Scheme 1