A series of molecular engineered organic glasses have been prepared to exploit the use of complementary Ar-Ar-F interactions to improve poling efficiency. These self-organized molecular glasses have also been used as host in the binary chromophore system to further improve the number density of chromophores and r(33) values. Ultrahigh r(33) values (up to 327 pm/V at the wavelength of 1310 nm) and good temporal stability could be achieved in these materials.