The third-order nonlinear optical properties have been investigated on the oriented blue- and red-form films of alkyl-urethane-substituted polydiacetylenes, by means of third harmonic generation (THG) and electro-absorption (EA) measurements. The spectra of \chi(3)(-3-omega;omega,omega omega)\ and Im chi(3)(-omega;0,0,omega) have been evaluated from the respective measurements. The results are discussed in terms of a three level model for quasi-one-dimensional excitons on the polymer backbone chains.