Polariscopy is demonstrated using hyperspectral imaging with a focal plane array (FPA) detector in the infrared (IR) spectral region under illumination by thermal and synchrotron light sources. FPA Fourier-transform IR (FTIR) imaging microspectroscopy is useful for monitoring real time changes at specific absorption bands when combined with a high brightness synchrotron source. In this study, several types of samples with unique structural motifs were selected and used for assessing the capability of polariscopy under this FPA-FTIR imaging technique. It was shown that the time required for polariscopy at IR wavelengths can be substantially reduced by the FPA-FTIR imaging approach. By using natural and laser fabricated polymers with sub-wavelength features, alignment of absorbing molecular dipoles and higher order patterns (laser fabricated structures) were revealed. Spectral polariscopy at the absorption peaks can reveal the orientation of sub-wavelength patterns (even when they are not spatially resolved) or the orientation of the absorbing dipoles.