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Thermo-optic coefficient dn/dT as well as volume expansion coefficients β of different polymer systems are measured for both TE and TM polarizations in an attenuated total reflection (ATR) configuration. Experimental results indicate that cross-linked polymer systems exhibit the thermal expansion coefficients smaller than those of the original side-chain systems. Moreover, the anisotropies in thermo-optic coefficients of the polymer systems with small birefringence exhibit linear relationship with the anisotropies in volume expansion coefficients, but the polymer systems with larger birefringence exhibit more complicated relationship.