The relaxation of polar order in a poled polymer system which had been designed in the context of nonlinear optical (NLO) materials was investigated. The isothermal relaxation of the Pockels effect as measured by the modulation of waveguide modes for different temperatures are best described by a symmetric Havriliak-Nagami relaxation time distribution. The width of the distribution increases with decreasing temperature. The temperature dependence of the mean relaxation time followed a modified version of the Vogel-Tamann-Fulcher equation. Thermally stimulated discharge current (TSDC) experiments were carried out in order to verify the proposed time-temperature behavior. The modified Vogel-Fulcher description of relaxation times describes the TSDC spectra well using the same relaxation time distributions as found for the isothermal relaxation.