These days, developing sustainable chemical facilities to generate biofuels, energy, bioproducts, and value-added chemicals has attracted attention. The above involves changing the traditional conception of transformation processes into more sustainable production based on the green chemistry principles, renewable energies, and the triple dimensions of sustainable development. Consequently, the addition of sustainability issues in process synthesis, analysis, and optimization of bioprocesses has become increasingly noteworthy. This study reports a literature review concerning the sustainable chemical process design framework based on process synthesis, analysis, and optimization methodologies. Studies on biorefinery/process synthesis approaches are analyzed and compared, offering a detailed overview of selected literature. These included hierarchical, mathematical, and mixed approaches. This review also outlined indexes and indicators for measuring sustainability in process design considering exergetic/energetic, environmental, economic, and safety aspects. It is worth mentioning the role that exergetic metrics are expected to play in measuring global process sustainability. Finally, the current research gap of process integration is analyzed, considering pinch analysis techniques, simultaneous heat and mass integration, and hybrid intensification−integration approaches.