Well-defined amorphous/semi-crystalline statistical copolymers of n-dodecyl isocyanate, DDIC, and allyl isocyanate, ALIC, were synthesized via coordination polymerization, using the chiral half-titanocene complex CpTiCl2(O-(S)-2-Bu) as initiator. In the frame of the terminal model the monomer reactivity ratios of the statistical copolymers were calculated using both well-known linear graphical methods and the computer program COPOINT. The molecular and structural characteristics of the copolymers were also calculated. The thermal properties of these samples were studied by Differential Scanning Calorimetry, DSC, measurements. The kinetics of the thermal decomposition of the statistical copolymers was studied by Thermogravimetric Analysis, TGA, and Differential Thermogravimetry, DTG, and the activation energy of this process was calculated employing several theoretical models. Moreover, block copolymers with the structure P[DDIC-b-(DDIC-co-ALIC)] were synthesized by sequential addition of monomers and coordination polymerization methodologies. The samples were characterized by nuclear magnetic resonance, NMR, spectroscopy, size exclusion chromatography, SEC, and DSC. The thermal stability of the blocks was also studied by TGA and DTG and compared to the corresponding statistical copolymers, showing that the macromolecular architecture greatly affects the properties of the copolymers. Thiol-ene click post-polymerization reaction was performed to introduce aromatic groups along the polyisocyanate chain in order to improve the thermal stability of the parent polymers.