To improve the risk decision-making effectiveness of enterprise safety professionals and curb the occurrence of unsafe behaviors, the theoretical connotation and improvement paths of risk cognitive ability were explored in this study. Based on SRK cognitive theory, the antecedent conditions of risk cognitive ability were classified into skill-based, rule-based, and knowledge-based cognitive abilities. The analysis of risk cognitive dimensions was combined from the perspectives of management systems, cognitive load, and cognitive tasks. Subsequently, a cognitive theoretical model was constructed, covering hazard identification ability, equipment operation ability, hidden danger inspection ability, hidden danger management ability, scenario decision-making ability, and case reasoning ability. NCA and fsQCA were applied to conduct data calibration, necessity analysis, sufficiency analysis, and robustness analysis on the multi-dimensional risk cognitive abilities of 100 safety professionals. Furthermore, the configurational paths of the antecedent conditions were analyzed, and targeted strategies for improving cognitive abilities were proposed. The results show that there are four configurational paths for both high risk cognitive competence and non-high risk cognitive competence. Specifically, high risk cognitive competence encompasses three configurational types: the rule-knowledge dual-driven type, the multi-dimensional cognitive ability synergistic type, and the emergency management ability dominated type. Accordingly, a “precision empowerment-multidimensional synergy-dynamic adaptation” path for improving risk cognitive ability is put forward, thereby enhancing the level of enterprise safety management.