Access to well-defined materials is one of the key requirements for successful implementation of block copolymer-based lithography for advanced semiconductor nodes. We report on the development of polystyrene-b-polytrimethylene carbonate (PS-b-PTMC) block copolymer (BCP) using organocatalytic ring opening polymerization of trimethylene carbonate (TMC) from hydroxyl-functional polystyrene macroinitiator as a materials candidate for directed self-assembly applications. The impact of organocatalyst choice and the extent of TMC conversion on the quality of PS-b-PTMC BCP were studied using gel permeation chromatography and nuclear magnetic resonance (NMR) spectroscopy techniques. As a direct method to identify PTMC homopolymer content in the resulting BCPs, a new NMR-based technique was developed. Finally, the influence of BCP purity on the thin film morphology was studied using atomic force microscopy and grazing incidence small angle X-ray scattering techniques. Our results indicate that the PTMC homopolymer impurity negatively impacts the thin film morphology, which is extremely important for lithographic applications.