Most of the advances in modern ceramics have been based on the development of a new material.A rational approach to the design and execution of such innovative syntheses can be made more scientific and less serendipitous. The understanding of molecular architecture and the principles of structure building can only be based on the science of crystal chemistry and solidstate thermodynamics. This review presents a summary of the principles and state-of-the-art empirical data in relevant crystal chemistry and the correlates found in phaseequilibrium diagrams. It dealsexplicitly with the role of metastable equilibrium in the formation and use of technological materials. It also summarizes the major classes of experimental facilities needed for sophisticated molecular engineering. Several examples are presented as successful paradigms of rational molecular engineerin covering different size ranges of creative architecture proposed as being based principally on 2-(or multi-) phase materials, andor on noncrystalline phases based on the entire composition range of ceramics, and on combinations of ceramics with metals and, possibly, polymers.from 10 f to 10 pm. Likely future developments in this areaare