Arene-perfluoroarene stacking interactions are explored in a new series of dendronized nonlinear optical (NLO) chromophores to create extended network structures and overcome intermolecular electrostatic interactions for improving their poling efficiency and alignment stability. These supramolecular self-assembled molecular glasses showed ultrahigh electro-optic (EO) activity (r 33 > 300 pm/V) and excellent thermal stability (at 85°C). These unprecedented EO activities could inspire the vigorous development of new integrated optical devices.Organic and polymeric electro-optic (EO) materials have been intensively studied for several decades due to their potential applications for the high speed/broad bandwidth information technologies (1-3), terahertz radiation generation and detection (4, 5), integrated circuitry, and multifunctional microand nanodevices (6-8). Their development is motivated not only by the large nonlinear optical (NLO) susceptibilities, but also by the versatility, ease of processability, and possibility of tailoring the physicochemical properties through In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.molecular engineering. Recently, significant advances (9, 10) in the design and synthesis of new-generation organic EO materials have led to the successful demonstration of ultralarge EO coefficients (r 33 values) of greater than 300 pm/V. This breakthrough result allowed organic NLO materials to significantly surpass the EO properties of lithium niobate, the dominant inorganic material currently used in modern EO modulator technology. These materials with such high EO activities and unprecedented performance in conventional device formats provide a powerful platform for building innovative devices such as hybrid systems using EO polymers integrated with silicon photonics (11,12).