A review and extension of process synthesis principles to inorganic chemicals and extractive metallurgical operations is presented. It is shown that the conceptualization of extractive metallurgy and inorganic chemical processes can be improved upon by the development of specific methodologies. The major issues analyzed are: 1) reaction path, 2) mineral processing circuit synthesis, 3) separation path using fractional crystallisation, 4) waste minimization and mass-exchange networks, 5) selection of mineral processing routes, and 6) synthesis of chemical induced separation. It is shown that there is a lack of methods for inorganic chemical and extractive metallurgy process synthesis, and that process synthesis has not found the place it deserves among the techniques used in inorganic chemical and extractive metallurgical operations. Research efforts conducted during the last few years, however, are a good beginning in the efforts to change this. A number of ideas are given to illustrate the potential applicability of process synthesis to this area. Several articles cited in this paper have been chosen from the chemical engineering literature which represent advances of particular interest in the inorganic chemical and extractive metallurgy process synthesis.