The Mn 2+ and Mo 6+ based Metal-mercaptoacetate (Metal-MA) hybrids were prepared by a simple acidbase 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 o C in N 2 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 (T d ), melting temperature (T m ) and molecular weight (M w ) of poly(ε-caprolactone) (PCL) were also investigated. The structure of PCL was comprehended by analysing its NMR spectrum. The activation energy (E a ) for the ROP of CL was determined as 10,363 Kcal/mol. A linear increase in M w of PCL with the increasing [M 0 /I 0 ] ratio was also noticed.