Crystalline silicon forms the basis of just about all computing technologies on the planet, in the form of microelectronics. An enormous amount of research infrastructure and knowledge has been developed over the past half-century to construct complex functional microelectronic structures in silicon. As a result, it is highly probable that silicon will remain central to computing and related technologies as a platform for integration of, for instance, molecular electronics, sensing elements and micro- and nanoelectromechanical systems. Porous nanocrystalline silicon is a fascinating variant of the same single crystal silicon wafers used to make computer chips. Its synthesis, a straightforward electrochemical, chemical or photochemical etch, is compatible with existing silicon-based fabrication techniques. Porous silicon literally adds an entirely new dimension to the realm of silicon-based technologies as it has a complex, three-dimensional architecture made up of silicon nanoparticles, nanowires, and channel structures. The intrinsic material is photoluminescent at room temperature in the visible region due to quantum confinement effects, and thus provides an optical element to electronic applications. Our group has been developing new organic surface reactions on porous and nanocrystalline silicon to tailor it for a myriad of applications, including molecular electronics and sensing. Integration of organic and biological molecules with porous silicon is critical to harness the properties of this material. The construction and use of complex, hierarchical molecular synthetic strategies on porous silicon will be described.