Nanostructures have received enormous attention due to their unique physical/chemical properties and promising applications in the fields of sensors and catalysis. While the optical, magnetic, catalytic, and electronic properties of nanoparticles and nanostructures are highly interesting, many applications are hampered by the lack of ability to assemble nanoparticles with controllable sizes, shapes, and interparticle spatial properties. This presentation reports the results of an investigation of the assembly of metal nanoparticles using fullerenes, dyes, proteins, and thioethers as mediators. Gold nanoparticles (1-100 nm) are studied as a model system. The combination of these building blocks allows the creation of an entirely new array of nanostructures with desired sizes and shapes. Characterizations of the nanostructured assemblies using various spectroscopic and microscopic techniques will be discussed. One important finding is that the interparticle spatial properties of the network nanostructures can be finely tuned, which could lead to novel optical properties for potential applications in biological/chemical sensing, controlled drug delivery, micro/nano electronics, and photosensitive or luminescent devices.