Films of polyetherketone doped with the chromophores Disperse Red 1 (DR1) and Disperse Red 13 (DR13) were prepared by spin-coating method. By the in situ Second-harmonic Generation (SHG) signal intensity measurement, the optimal poling temperatures were obtained. For the investigated polyetherketone polymer doped with DR1 (DR1/PEK-c) and polyetherketone polymer doped with DR13 (DR13/PEK-c) films, the optimal poling temperatures were 150degreesC and 140degreesC, respectively. Under the optimal poling conditions, the high second-order nonlinear optical coefficient chi(33)((2)) = 11.02 pm/V has been obtained for the DR1/PEK-c; and for DR13/PEK-c at the same conditions the coefficient is 17.9 pm/V. The SHG signal intensity DR1/PEK-c could maintain more than 80% of its initial value when the temperature was under 100degreesC, and the SHG signal intensity of the DR13/PEK-c could maintain more than 80% of its initial value when the temperature was under 135degreesC.