Process synthesis and intensification are well-known and powerful tools for the development of chemical processes with improved energy and cost efficiency. However, even though a combination of both provides the most potential for exploiting these improvements, process synthesis still focuses on classical unit operations, while intensified process options are rather delayed and considered mainly for retrofitting. This not only limits the result of process synthesis but also impedes the application of intensified process options, as they need to justify additional investment for process modification. In order to reveal improved process options and reduce the barrier for intensified processes, the current article presents a process synthesis approach which generates thermodynamically feasible phenomena-based flowsheets by means of superstructure optimization. The approach provides maximum flexibility for integrating and modifying the involved phenomena building blocks, which only afterward are interpreted and translated into equipment that represents the final process. Innovative hybrid process configurations and intensified equipment can thereby be synthesized automatically in conceptual design. The current article introduces the general concept and the implementation for an initial set of phenomena building blocks. Successful application of the approach is demonstrated for the nonreactive but thermodynamically nonideal case study of ethanol dehydration.