The service performance of chromium-free zinc–aluminum coatings exhibits characteristics from multiple perspectives. Fully considering the physical properties, corrosion resistance, and economic viability of the coatings, this study incorporates the concepts of “domain” and “degree” from extenics theory into the analytic hierarchy process to optimize the formulation of chromium-free zinc–aluminum coatings. The findings reveal that the extension analytic hierarchy process takes into account the diversity of evaluation indicators, enhancing the objectivity and accuracy of the comprehensive evaluation results. Nine formulations were developed using a four-factor, three-level orthogonal experiment to evaluate the effects of metal powder, PEG-400, KH-560, and sodium molybdate on the service performance of chromium-free zinc–aluminum coatings. Utilizing an extensible hierarchical sorting weight system alongside a performance index grading and scoring method, 3# emerged with the highest score, indicating the best overall performance. The research outcomes offer innovative insights and technical support for optimizing the formulations of chromium-free zinc–aluminum coatings and other coatings.