Two different procedures for the preparation of bimorph structures within nonlinear optical polymer layers are reported. One technique consists of thermally assisted poling above the glass-transition temperature followed by photo-induced poling below the glass-transition temperature. In this poling scheme, the second step is based on the photoisomerization of the dipole molecules. The other method comprises two consecutive thermally assisted poling steps with opposite field polarity in a double layer of two nonlinear optical polymers with different glass-transition temperatures. Pyroelectric thermal analysis is employed for analyzing the stability of the resulting bimorph structures, while pyroelectric depth profiling allows for a non-destructive qualitative analysis of their polarization distributions.