Process safety management (PSM) in the transition toward sustainability has garnered increasing attention in the emerging era of Industry 5.0 (I5.0). This study provides an inclusive proposal for a sustainable process safety management 4.0 (SPSM 4.0) framework, concentrating on its evolution, drivers, and a comprehensive framework highlighting structures and applications. The core values of I5.0 (sustainability, human‐centricity, and resilience) and advanced technologies like artificial intelligence (AI), industrial Internet of things (IIoT), and cyber‐physical systems (CPS) are integrated with the PSM system. SPSM 4.0 aims to alter the PSM ecosystem through the applications of digital transformations at workplace by ensuring the process safety, well‐being of employees and assets while leveraging socioeconomic environmental concerns at an improved efficiency. The proposed framework bridges the gap between PSM and sustainability, which serves as a foundation stone for future SPSM 4.0 guidelines targeted at practitioners, policymakers, and academicians. In addition, the study proposes a comprehensive umbrella paradigm integrating PSM with sustainability pillars in an I5.0 landscape. Concluding, the research focuses on a critical discussion of the decision support system operationalizing the SPSM 4.0 system and suggesting critical takeaways for the managers and researchers.