This thesis focuses on the synthesis and characterization of Poly(ε-caprolactone) (PCL) and its block copolymers, Poly(ε-caprolactone)-b-Poly(4-hydroxyvalerate) (PCLb-P4HV) and Poly(ε-caprolactone)-b-Poly(δ-valerolactone) (PCL-b-PVL). These polymers were synthesized through ring-opening polymerization of various lactones (εcaprolactone, γ-valerolactone, and δ-valerolactone) using biocatalysts such as citric acid, glycolic acid, salicylic acid, boric acid and acetic acid. Detailed analytical and thermoanalytical characterizations were performed. Differential Scanning Calorimetry (DSC) showed that most homopolymers and copolymers exhibited crystallization (Tc) and melting temperatures (Tm) varying between 5-25oC and 50-65oC respectively, confirming successful polymerization. DSC thermograms of block copolymers revealed that solvent choice for precipitation affected crystallinity and thermal properties, with a small second melting point observed due to different crystalline forms. Fourier Transform Infrared Spectroscopy-Attenuated Total Reflectance (FTIRATR) confirmed the homopolymerization of Poly(ε-caprolactone) using citric, glycolic, and salicylic acids. Mass spectrometry further revealed characteristic peaks corresponding to expected molecular weights and compositions of the copolymers. The presence of these peaks corroborated the formation of block copolymers with distinct blocks of PCL, P4HV, and PVL confirmed the molecular integrity of the synthesized block copolymers. This thesis provides a comprehensive analysis of the synthesis and characterization of block copolymers, offering insights into their structural properties and potential applications. The findings contribute to the understanding of the polymerization process and the properties of the resulting materials, which are significant for industrial and biomedical applications. The resultant copolymers were utilized in Melt Electrowriting process to provide tissue scaffold. Despite their brittleness, all copolymers were electrowritten without issues, indicating their potential interest in tissue engineering applications