The orientation relaxation of azo-dyes upon all-optical poling was studied. Azo-dye doped amorphous polymers were poled for different durations by all-optical poling at several temperatures. A quasi-permanent macroscopic second-order nonlinear optical susceptibility chi((2)) was inscribed in the dye-doped centrosymmetric polymer systems. Relaxation of the chi((2)) was monitored by second harmonic generation. It shows that the polar orientation relaxation follows the duration of the poling process: the longer the poling, the slower the polar relaxation time. Causes of the orientation relaxation retardation are discussed. (c) 2006 Elsevier B.V. All rights reserved.