This study is the first to provide a systematic approach to assessing the potential of advanced reactive distillation technologies to expand the applicability of reactive distillation. The work presented here focuses on the synthesis of advanced reactive distillation technologies, proposing a conceptually based methodology for early-stage screening. The methodology uses basic thermodynamic and kinetic data to navigate a decision-making flowchart in four steps: compositions and splits, basic properties and operating windows, kinetics, and phase equilibria. The results qualify advanced reactive distillation technologies as advantageous, technically feasible, or not applicable. Five industrially relevant case studies illustrate the application of the methodology to develop preliminary process flowsheets. The proposed methodology aims to guide technology selection using basic data while providing flexibility to meet the objectives of the design problem. This methodology contributes to integrating a technology-oriented approach normally followed in process intensification studies into a process systems engineering approach by developing a conceptual flowsheet in the early stages of process design.