Display omitted •Deterministic modeling of cationic ROP of ε-CL based on the method of moment.•Revealing the effect of transesterification reaction on molar mass averages of PCL.•Applying the developed model to metal free ROP system catalyzed by TrBF4.•Playing with process conditions to increase the industrial sustainability of PCL synthesis. Ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) is an efficient way to produce a widely used biodegradable polymer, i.e., poly(ε-caprolactone) (PCL). Compared to coordination ROP, ionic ROP receives great attentions in recent years due to mild reaction conditions and well-defined polymer microstructure. To fully exploit the potential of ionic ROP, in this work, a mathematical kinetic model for activated monomer mechanism (AMM) based cationic ROP of ε-CL was developed based on method of moments (MoM). Using the developed model, we estimated the values of the kinetic coefficients of monomer activation and monomeric units’ protonation reactions. The simulated results are found to be in good agreement with experimental data, as well as the benchmark by kinetic equation. Moreover, the simulations reveal the crucial role of transesterification reaction in molar mass distribution broadening and how the concentrations of acid and alcohol affect the monomer conversion and average molar masses of the polymer. Finally, the model was successfully extended to a newly reported system using trityl tetrafluoroborate (TrBF4) as catalyst, proving the universality of our model. This study provides deeper understanding of the cationic ROP and allows to optimize process conditions to increase the industrial sustainability of PCL-based materials.