The preparation of new nanomaterials requires hierarchical levels of ordering and structuring: from molecular to macroscopic. Much has been demonstrated in metal, metal oxide, inorganic nanoparticles by way of size, shape, and polydispersity control. The Plasmonic and emissive properties dependent on size, shape, and hot spots are well known. Dendrimers and other hyperbranched polymer systems are of interest for their functionality in catalysis, drug delivery, reactivity, etc. Of high interest are dendrimer functionality in electro-optical applications and nanopatterning. This includes dendrimers capable of hierarchical ordering and self-assembly. We highlight the convergent synthesis of a variety of hybrid nanoparticle dendrimers and their electropolymerizability. The synthesis of precise dendrons as modular building blocks for functional dendrimers and the use of star copolymers for various core-shell architectures are demonstrated. Our group has reported a number of these hybrid systems and have reported the step-by-step routes towards structure-property relationships. These has resulted in controlled charge -transfer and energy transfer properties not to mention the ability to provide greater stability for these nanoparticles. What is also important is the use of surface sensitive spectroscopic and microscopic analytical tools applied rationally to highlight evidence of order and function.