The molybdenum thioglycolate (Mo-TG) end capped poly(ε-caprolactone) (PCL) was prepared in the presence of novel Mo-TG nanohybrid initiator by ring opening polymerization (ROP) technique. The structural analysis was carried out by FTIR, 1H and 13C NMR techniques for the synthesized PCL. The particle size of the end capped Mo-TG nano hybrid in the PCL matrix was analysed by HRTEM. The morphology, surface roughness and average surface roughness of the polymer sample were investigated by AFM. The geometry of the nucleated crystals of PCL was examined using polarized optical microscopy (POM). The crystallization and thermal history of the sample under non-isothermal condition were assessed by DSC and TGA. The morphology of the nucleated crystals was analysed theoretically with the help of kinetic models for Mo-TG end capped PCL under non-isothermal crystallization condition. The kinetic parameters associated with crystallization and degradation processes of PCL were also determined using various kinetic models.