Second-order nonlinear optical polymers must be poled in order to achieve the required non-centrosymmetry. Periodically poled materials are required for phase-matched operation of polarization converters1 and parametric devices2. For second-harmonic generation with modes of different order1, three-dimensionally (3-D) poled patterns are needed to optimize the overlap integral, as suggested by Akhmediev and Novak3. As the poled polymer is in a metastable state, the partially aligned dipoles relax, thus limiting the lifetime of the poled polymer. Easy-to-use experimental methods, which allow for the investigation of dipole relaxation as well as periodical and 3-D dipole patterns, are highly desirable. It will be shown that the recently developed techniques of Pyroelectrical Thermal Analysis (PTA), Scanning Pyroelectrical Microscopy (SPM), and Pyroelectrical Depth Profiling (PDP), respectively, are almost ideal solutions for these tasks.