The electrode contact poling is one of the efficient tools to induce a stable polar order of nonlinear optical (NLO) chromophores in the solid film. Self-assembled NLO chromophores with high electro-optic (E-O) activities were utilized for quantitative determination of the chromophore order induced under contact poling by spectroscopic changes. We found that NLO chromophores rarely decompose under the high electric field during contact poling. The absorption spectra were de-convoluted into a sum of Gaussian components to separate energy transitions for a binary composite system which contains a secondary guest chromophore AJC146 in the self-assembled chromophore HDFD. Poling efficiency was significantly improved in the binary system compared to the individual components.