Although controlled/living radical polymerization processes have significantly facilitated the synthesis of well-defined low polydispersity polymers with specific functionalities, a detailed and systematic knowledge of the thermal stability of the products highly important for most industrial processes is not available. Linear polystyrene (PS) carrying a trithiocarbonate mid-chain functionality (thus emulating the structure of the Z-group approach via reversible addition-fragmentation chain transfer (RAFT) based macromolecular architectures) with various chain lengths (20 kDa <= M-n,M-SEC <= 150 kDa, 1.27 <= D = M-w/M-n <= 1.72) and chain-end functionality were synthesized via RAFT polymerization. The thermal stability behavior of the polymers was studied at temperatures ranging from 100 to 200 degrees C for up to 504 h (3 weeks). The thermally treated polymers were analyzed via size exclusion chromatography (SEC) to obtain the dependence of the polymer molecular weight distribution on time at a specific temperature under air or inert atmospheres. Cleavage rate coefficients of the mid-chain functional polymers in inert atmosphere were deduced as a function of temperature, resulting in activation parameters for two disparate M-n starting materials (E-a = 115 +/- 4 kJ.mol(-1), A = 0.85 x 10(9) +/- 1 x 10(9) s(-1)) M-n,M-SEC = 21 kDa and E-a = 116 +/- 4 kJ.mol(-1), A = 6.24 x 10(9) +/- 1 X 10(9) s(-1), M-n,M-SEC = 102 kDa). Interestingly, the degradation proceeds significantly faster with increasing chain length, an observation possibly associated with entropic effects. The degradation mechanism was explored in detail via SEC-ESI-MS for acrylate based polymers and theoretical calculations suggesting a Chugaev-type cleavage process. Processing of the RAFT polymers via small scale extrusion as well as a rheological assessment at variable temperatures allowed a correlation of the processing conditions with the thermal degradation properties of the polystyrenes and polyacrylates in the melt.