Herein, we present the CROP of DOT. A detailed comparison of initiators and reaction conditions showed that quantitative monomer conversion and low dispersities (1.5 < Ð < 2.0) could be obtained without the need for inert atmosphere or even dry solvents. The resulting DOT homopolymers degraded quantitatively under various conditions, including through aminolysis, thiolysis or simple heating with or without solvent. The respective mechanisms are discussed with polymers showing unzipping through controlled depolymerization. Interestingly, the choice of initiator had a profound impact on the thermal stability of pDOT polymers with methyl triflate (MeOTf)-initiated polymers showing a much lower onset of thermal depolymerization. The depolymerization of pDOT produces the thiolactone isomer of DOT as sole/main degradation product making this system promising for chemical recycling.