In this paper, we report our recent developments in achieving thermally stable polyimides that possess large second order nonlinear optical activity. We have developed several classes of novel chromophores based on the combination of efficient thiophene conjugating units and novel electron-donating and electron-accepting functional groups. Through these developments, we have synthesized chromophores that possess non-resonant βμ values as high as 9,100 × 10−48 esu measured at 1.9 μm. These chromophores also possess improved thermal and chemical stabilities. The incorporation of these chromophores in high temperature polyimides produces E-O Materials with high linear electro-optic coefficients (in excess of 15 pm/V at 1.3 μm) and long-term temporal stability at an elevated temperature of 150°C for more than 800 hours.