Binary chromophore systems represent a new and very promising class of organic second-order nonlinear optical (electro-optic) materials, where favorable intermolecular electrostatic interactions lead to significantly enhanced electro-optic coefficients and to other favorable physical properties such as low optical loss and improved stability. In this report, laser-assisted poling of a binary chromophore system consisting of a photoaddressable chromophore host (DR-1-co-PMMA) containing a non-photoaddressable guest chromophore (YLD_124) is demonstrated. A factor of 2.5 enhancement in poling efficiency of the guest chromophore (compared to simple conventional electric field poling of the same material) is observed when polarized light is used to selectively enhance the order of the host chromophores. These results further emphasize the importance of favorable intermolecular interactions thought to exist between guest and host chromophores in binary chromophore containing materials. Thin-film samples were pro...