The growth of 4-(N,N-dimethylamino)-3-acetamidonitrobenzene (DAN) crystals on nanostructured poly(tetrafluoroethylene) (PTFE) substrates has been investigated by means of x-ray, micro-FTIR (Fourier-transform infrared) and nonlinear optical ellipsometry techniques. Two types of structural arrangements were identified, depending on growth conditions. In both cases, the (001)(DAN) plane contacts the (100)(PTFE) substrate plane. The major difference between both types of samples lies in the degree of azimuthal orientation at the interface. For thin samples (thickness < 0.3 mu m), the average direction of the a crystallographic axes of the DAN crystals lies parallel to the [001](PTFE) direction with a broad angular distribution, while thick samples (thickness > 1 mu m) are characterized by a uniaxial orientation with an isotropic random distribution in the plane of the layers. The comparison between various techniques used in this study to characterize the obtained thin films showed a remarkable agreement. In this context, second-harmonic generation was revealed once again as a powerful technique toward the study of orientation effects in crystalline layers of NLO organic materials, much beyond the possibilities of traditional linear polarization methods.