Chemical processes are complex dynamic systems. With the chemical industry under pressure to introduce improvements through the greater use of automation and intelligence, the need for comprehensive reliability evaluation has become more urgent both theoretically and practically. The employment of intelligent algorithms based on factory data has been the recent research hotspots. But for complex systems with available data on a smaller scale, reliability evaluation models have suffered on such problems as a result of instability and over-fitting, which have to be resolved. The GRA-GA-BP-MCRC hybrid algorithm was proposed. It combined the two-step genetic algorithm (GA)-back propagation (BP) and grey relational analysis (GRA) with Markov chain residual correction (MCRC). Based on the technical characteristics and the management demands, 46 influential factors of process reliability were introduced, which covered man, machine, material, method, and environment. For model convergence to be assured, GRA and attribute reduction rule were introduced. Meanwhile, based on the correlation of the factors, the two-step GA-BP was proposed to resolve the over-fitting problem of artificial neural network with complex input parameters. As well, MCRC was applied to modify the GA-BP error. The resulting average relative error of the hybrid algorithm was 2.36%, while the conventional algorithm was 10.28%.T he Internet of things, big data, artificial intelligence, and mobile intelligent terminals are enabling new operation modes in the chemical industry. Cyber-physical systems allow enterprises to exhibit enhanced perception, analysis, prediction, coordination, and optimization, and the use of intelligence becomes the most important capability to improvements. Some scholars have introduced the concept of an intelligent factory 1,2 in which the online management of health, safety, and environment (HSE) is one of the most important requirements. 3-5 HSE evaluation models have become essential models for enterprises to continuously improve through using intelligent measures.System reliability is one of the important factors to evaluate the HSE state of chemical industries and the system's probability of completing assigned tasks under certain conditions without fault. 6,7 Progress has been made in reliability theories applicable to the chemical industry. Saleh researched reliability theories of complex systems. 8 Gheorghe introduced the integrated regional risk assessment and safety management for energy and several complex industrial systems. 9 Gang presented a novel condition-based maintenance system that used a reliability-centered maintenance mechanism to optimize maintenance cost, and employed data fusion strategy to improve condition monitoring, health assessment, and prognostics. 10 Liu established the fault-oriented reliability model to evaluate chemical systems for safety, environment, and economics. 11 However, these reliability models of chemical systems also have limitations under complex conditions in which there are vari...