In this study, an integrated vector-based three-dimensional (3D) methodology for the life cycle sustainability assessment (LCSA) of chemical process alternatives is proposed. In the methodology, a 3D criteria assessment system is first established by using the life cycle assessment, the life cycle costing, and the social life cycle assessment to determine the criteria from the environmental, economic, and social pillars, respectively. The methodology incorporates the analytic hierarchy process (AHP) method to convert experts' judgments on the soft criteria into quantitative data and restive a unitary scale for both quantified soft criteria and normalized hard criteria. After assigning appropriate weights to each pillar and criterion by using the AHP method, the sustainability of the alternative processes can be prioritized by employing a novel vector-based algorithm, which combines the absolute sustainability performance and the relative sustainability deviation of the investigated processes. A case study on the sustainability assessment of three alternative ammonia production processes demonstrates that the proposed methodology is able to serve as a comprehensive and rigorous tool for the stakeholders to rank and identify the most sustainable chemical process alternatives.