Nonlinear optical properties of two thiophene-based conjugated polymers (PTT and PDTB) were studied by the photoinduced absorption spectroscopy and the third harmonic generation spectroscopy. The results obtained with these two methods are used to estimate the value of χ(3) in these materials. Resonant χ(3) are (2.0 ± 0.2) × 10−11 e.s.u. and (1.0 ± 0.1) × 10−11 e.s.u. for PTT and PDTB, respectively. χ(3) is shown to be related to the width of the optical gap through a sixth-power law. In PTT a vibronic structure due to the C = C stretching mode appears in the χ(3) spectrum.