Recent development of dendron-containing NLO chromophores and polymers is summarized. By modifying the chromophore shape or applying the site isolation principle to these materials, we have systematically build up our understanding of how to molecular engineer the NLO materials. In this process, we have introduced the dentritic structures to these materials, varied from 3-D shaped dendritic chromophore, to fully-functionalized dendrimers with the center cores of NLO chromophores and crosslinkable periphery, and to side-chain dendronized NLO polymers. Compared to the conventional designed organic NLO materials, these nanoscale tailored NLO chromophores and macromolecules provide great opportunities for the simultaneous optimization of macroscopic electro-optic activity, thermal stability, and optical loss.