A generalized modeling framework for process synthesis alternatives is proposed, based on fundamental mass/heat-transfer principles. A multipurpose mass/heat-transfer module is introduced as the building block of the framework, whereas basic block-superstructure rules (such as splitting, mixing, and bypassing) are used to develop a systematic representation of process units and process structures, conventional or not. Process synthesis procedures are explored within this modeling framework, where synthesis alternatives are not postulated as process unit networks, but explored simultaneously without predefining synthesis schemes, as combinations of mass/heat-exchange stream matches. The representation potential of this framework is illustrated with examples from unit operations, whereas synthesis example problems are presented to show the broad range of process alternatives that can be modeled, identified, and optimized.