artificial intelligence/machine learning (AI/ML), cloud-based services, telemedicine, and autonomous vehicles, as well as, demands from remote work due to the COVID-19 pandemic. To keep pace with demand for optical and wireless communications, there is an urgent need for electro-optic modulators with large bandwidths, high power-efficiency, and micrometer-scale footprints that enable dense chip-scale integration with complementary metal-oxide-semiconductor electronics. [1][2][3][4] Significant improvements in device performance have been made by silicon-organic hybrid [5][6][7][8][9][10][11][12][13][14] and plasmonicorganic hybrid. [1,[15][16][17][18][19][20][21][22][23][24][25][26][27] Pockels effect modulators, which have proven to be effective photonic platforms for both analog and digital applications.Achieving groundbreaking performance requires synergistic innovation from rational design of organic electrooptic (OEO) materials to device engineering and advancements in communication systems. [20,[28][29][30] As the active component for the Pockels effect, OEO materials, using conjugated π-electron systems, deliver large EO coefficients > 300 pm V −1 (>10× lithium niobate), low dielectric constant (static ε < 7), and femtosecond (<30 fs) response times. [28] Large EO coefficients (r 33 ) of organic material require a combination of high chromophore hyperpolarizability (β), electric field poling-induced acentric order of the chromophores (), and chromophore number density (ρ N ). Furthermore, the EO modulator operating voltage is strongly dependent on the refractive index of the material (n) at the operational wavelength: The half-wave voltage-length parameter V π L for an EO modulator is inversely proportional to n 3 r 33 . Furthermore, n increases with β and ρ N . [28,29] The past two decades of research and development have demonstrated many effective molecular engineering strategies to increase ρ N (increasing ρ N by eliminating the inactive polymer host, while maintaining good poling efficiency). These strategies include side-chain engineering, site-isolation, self-assembly, multi-chromophore dendrimers, chromophore blending, and control of chromophore shape. [31][32][33][34][35][36][37][38][39][40][41] These strategies, led to materials with enhanced r 33 (300-550 pm V −1 at 1310 nm wavelength), [31,35,36,[42][43][44][45][46] which is a large improvement over lithium niobate (≈30 pm V −1 ), High performance organic electro-optic (OEO) materials enable ultrahigh bandwidth, small footprint, and extremely low drive voltage in silicon-organic hybrid and plasmonic-organic hybrid photonic devices. However, practical OEO materials under device-relevant conditions are generally limited to performance of ≈300 pm V −1 (10× the EO response of lithium niobate). By means of theory-guided design, a new series of OEO chromophores is demonstrated, based on strong bis(4-dialkylaminophenyl)phenylamino electron donating groups, capable of EO coefficients (r 33 ) in excess of 1000 pm V −1 . Density functi...