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This paper reports that the thermo-optic coefficient (dn/dT) as well as thermal expansion coefficients (β) of DR1/PMMA polymer film are measured for both TE (transversal electric) and TM (transversal magnetic) polarizations by using an attenuated total reflection configuration at the wavelengths of 832nm. The thermo-optic coefficients of DR1/PMMA are negative and as high as the order of 10-4/°C. The influences of dopant concentration, poling process and photobleaching process on the thermo-optic properties of DR1/PMMA are also investigated.