This work is targeted to study emulsion polymerization of vinyl chloride monomer (VCM) using experimental and mathematical methods. To fulfill this goal, a computer code was developed on the basis of zero-one population balance by which the effects of initiator and emulsifier concentration on the evolution of VCM conversion were investigated in the course of polymerization. The model was also trained to capture the coagulation of the particles. This enabled to adopt a reliable way of evaluating the particle size distribution (PSD). In particular, the rates of homogeneous and micellar nucleation mechanisms were simulated and reasonably predicted alterations in the PSD and the number of polymer particles under the influence of aforementioned parameters. The results from modeling were satisfactorily consistent with the experimental outputs and obviously visualized the impact of initiator and surfactant concentration on the PSD of the prepared PVC latexes.