Accessibility to new synthetic materials to sub‐nanometer levels to quantum scales is not trivial—TiO2 is a case in question. The evolution of some biominerals with equilibrium morphologies stabilized by ligand compartmentalization enabling control over shape and size reveals mechanistic clues to engineer biomimetic approaches. Using the principles of biomimicry it is shown that the quantum confinement of TiO2 to 0.8–2 nm can be achieved through the manipulation of a synthetic amorphous precursor using low temperature annealing and an alkyl rich multi‐elemental reaction environment. This establishes a new route to material tunability and accessibility to quantum sub‐bands that show a profound interdependence on anisotropic growth patterns. energy materials. For more details, see the Concept by V. Khare et al. on page 8104 ff.