In this article, we first explicate the pivotal role that emergency firefighting and rescue capabilities play in petrochemical enterprises for addressing sudden disaster incidents. Building upon the current state of assessment for such capabilities within China’s petrochemical sector, we succinctly analyze the strengths and deficiencies inherent in various evaluative methods and models. The assessment of firefighting and emergency rescue capabilities in petrochemical enterprises is a complex data processing task that involves the interaction of multivariate data and integrates both subjective and objective elements. Drawing on a multivariate data coupling modeling approach, this study proposes a comprehensive assessment model for the emergency firefighting and rescue capabilities of petrochemical plant areas. This model synthesizes the Analytic Hierarchy Process (AHP) and the Decision Making Trial and Evaluation Laboratory (DEMATEL) methods to establish composite weights, coupled with a Grey Relational Analysis (GRA). The assessment framework is constructed on four primary indices: plant area safety management, infrastructure, the grade of fire stations, and the siting of fire stations; it further includes seven secondary and twenty-nine tertiary indices. Employing the principle of minimum discrimination information, composite weights are determined through the AHP and DEMATEL methods. Subsequently, these weights are integrated with the grey relational coefficients derived from GRA to rank the indices, and based on a set of evaluative statements, analytical results and recommendations for improvement are presented. Applying this model, the firefighting and emergency rescue capabilities of a petrochemical plant area were assessed, yielding a final rating of “Good”. This outcome is consistent with results obtained from an AHP-fuzzy comprehensive evaluation method based on the same dataset. However, our proposed method allows for a detailed differentiation in areas identified as deficient.