Conventional HAZOP is a collaborative and multidisciplinary activity to identify the hazards associated to operability of the chemical processes. Then the consequences and required safeguards of each potential deviation or failure are assessed qualitatively one by one. It is performed with the assumption of “one failure at the time” for the process parameters. Furthermore, process complexities such as multiple failures, domino effects, time and amplitude dependent deviations etc. are avoided to keep the HAZOP brainstorming sessions systematic and effective. Therefore, the quality and outcomes of HAZOP study are relatively subjective and depend on the experience and competency of the HAZOP team. This simplified approach cannot fully cover the hazard identification and risk assessment of the complex processes such as polymerization. Furthermore, the incident investigations show that almost all major accidents have occurred due to multiple failures or domino effects. This paper aims at developing a practical methodology in the context of “Industry 4.0” and particularly illustrate how dynamic simulation liberates the HAZOP team from the simplification assumptions such as one failure at the time or neglecting the domino effects during the lifecycle of the complex processes. An industrial styrene bulk free radical polymerization process has been chosen as the case study to depict the applicability of the proposed method. In continuation of this research, the dynamic simulation integrated with Artificial Intelligence (AI) algorithms and Multivariable Process Monitoring (MPM) together with virtual collaboration tools will be invoked towards a more practical and effective HAZOP 4.0 platform. Such a platform can be the foundation of the further Process Safety Management (PSM) elements such as “Operating manuals”, “Training and Competency management”, “Condition monitoring and predictive maintenance”, “Management of Change”, “Pre-Start-up Safety Review”, etc.