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We present a dynamic risk-based process design and multi-parametric model predictive control optimization approach for real-time process safety management in chemical process systems. A dynamic risk indicator is used to monitor process safety performance considering fault probability and severity, as an explicit function of safety–critical process variables deviation from nominal operating conditions. Process design-aware risk-based multi-parametric model predictive control strategies are then derived which offer the advantages to: (i) integrate safety–critical variable bounds as path constraints, (ii) control risk based on multivariate process dynamics under disturbances, and (iii) provide model-based risk propagation trend forecast. A dynamic optimization problem is then formulated, the solution of which can yield optimal risk control actions, process design values, and/or real-time operating set points. The potential and effectiveness of the proposed approach to systematically account for interactions and trade-offs of multiple decision layers toward improving process safety and efficiency are showcased in a real-world example, the safety–critical control of a continuous stirred tank reactor at T2 Laboratories.