The Mn2+ and Mo6+ based Metal-mercaptoacetate (Metal-MA) hybrids were prepared by a simple acid-base titration method. The prepared Metal-MA hybrids were analysed by FT-IR spectroscopy, UV-visible spectroscopy, SEM, particle size analyser (PSA), XRD and EDX. The prepared Metal-MA hybrids were investigated to assess their catalytic activity for ring-opening polymerization (ROP) of ε-caprolactone (CL) in the absence of an initiator at 160 oC in N2 atmosphere by varying the catalyst concentration and temperature. The catalytic activity of the Metal-MA hybrid towards the ROP of CL was concluded by the FTIR-RI method. The % yield, degradation temperature (Td), melting temperature (Tm) and molecular weight (Mw) of poly(ε-caprolactone) (PCL) were also investigated. The structure of PCL was comprehended by analysing its NMR spectrum. The activation energy (Ea) for the ROP of CL was determined as 10,363 Kcal/mol. A linear increase in Mw of PCL with the increasing [M0/I0] ratio was also noticed.