The photoinduced reorientation and photoelectropoling processes were investigated in molecular films of aliphatically substituted azobenzenes. While polarized illumination leads to a conversion of isotropic samples into anisotropic ones, upon application of external electric fields even macroscopically polar materials are created. The macroscopic polarity can be reversed under suitable experimental conditions. Order parameters as a function of the poling field were determined by Stark spectroscopy. Using atomic force microscopy it is shown that the structure of the sample is well defined on a microscopic length scale, whereas on a macroscopic length scale it is not.