Recent developments of molecular architectural control and solid-state engineering have led to exceptionally large electro-optic (EO) activities in organic and polymeric nonlinear optical (NLO) materials. A new generation of NLO dendrimers has been developed to generate well-defined nano-objects, minimize strong intermolecular electrostatic interactions, and improve poling efficiency and stability. A facile and reliable Diels-Alder "click" reaction was applied for lattice hardening to improve physical properties of cross-linkable EO polymers. The "click" chemistry also provides means to study the relationship between EO activity, chromophore shape, and number density of the chromophore, systematically. The NLO dendrimers or polymers were used as hosts for guest chromophores to increase chromophore concentration and improve poling efficiency. A variety of nanostructured organic and polymeric materials with ultrahigh r33 values (>350 pm/V at the wavelength of 1310 nm, more than 10 times mat of LiNbO3) and excellent temporal alignment stability at 85 °C were achieved by the approaches.