We have developed two new classes of highly active and thermally stable nonlinear optical (NLO) chromophores based on the use of efficient thiophene conjugating units, a N,N-diphenylamino electron-donating group, and a 1,1′-dicyanovinyl substituted electron-accepting group. We have also developed a facile and generally applicable method to functionalize NLO chromophores onto high temperature polymers to demonstrate both high electro-optic (E-O) coefficients and long-term alignment stability at 100 °C.