-Abstract- Although chemical synthesis has evolved to a relatively advanced state, the ability to prepare well-defined materials of controlled shape, size, and structural hierarchy on the 10 nm – 10 micron length scale is still in its relative infancy and currently remains the virtually exclusive domain of biology. In this talk the development of a promising new route to such materials, termed “crystallization-driven self-assembly” (CDSA), will be described. This approach was discovered as a result of an investigation of the solution self-assembly behavior of block copolymers with crystallizable core-forming polyferrocenylsilane metalloblocks. CDSA offers an interesting and potentially powerful new route to well-defined micelles and hierarchical terials with controlled dimensions and a variety of potential applications. The CDSA approach is also extendable to a wide range of other crystalline core-forming blocks, including biorelevant and π-conjugated materials.