Accidents in process industry occur frequently with serious casualties and property losses. This paper builds an accident causation model of process industry based on system thinking by dividing the accident causation system into 4 subsystems and 22 factors. A combination of grey relational analysis and correspondence analysis is conducted to carry out a structured analysis of the collected data. The research contains three main parts: (1) Grey relational analysis is used to obtain the significance ranking of 22 cause factors in process industry, and three critical cause factors are identified as “Security inspection,” “Risk identification,” and “Security awareness.” (2) Through correspondence analysis, the correlations between three sets of variables are analyzed and the cause factors requiring focused attention are identified as “Electric spark,” “Temperature,” “Raw material control,” “Punching phenomenon,” “Equipment clogging,” and “Combustible gases.” (3) An intelligent monitoring scheme is developed for the critical factors of each subsystem, which aims to achieve real‐time monitoring and early warning by means of video surveillance and sensor placement for the human, equipment, and environment subsystems. The conclusions obtained from this study can be used to enhance the efficiency of safety management and reduce the probability of accident occurrence in the process industry.