Integrative chemistry is the link between the notions of “complexity in chemistry” and the bio-inspired integrative synthesis. This chapter relies on this vein of integrative chemistry, while dealing with sol-gel chemistry. Through the sol–gel-based integrative chemistry, it shows how it is possible to trigger materials dimensionality and beyond their functionalities when reaching enhanced applications. Thereby it selectively proposes the morphosyntheses of discrete objects, 1D materials (fibers), 2D arrays (films), and 3D macrocellular foams bearing hierarchical porosities (monoliths). The chapter discusses in detail how integrative chemistry allows fine-tuning of material shapes and dimensions while offering enhanced applications. Considering the shaping modes, it also deals with how the integrative chemistry allows positioning the chemical reactors within the geometric spaces, with specific competence appearing as a novel paradigm with regard to traditional sol-gel chemistry.