We investigated anisotropic optical behavior in solid-state materials using Fourier transform infrared reflection microspectroscopy in combination with polarization modulation. For a Ca1.8Sr0.2RuO4 crystal with an isotropic optical surface, we found the reflection difference to be very close to zero, independent of the azimuthal angle of the sample. A Ca1.4Sr0.6RuO4 crystal with an anisotropic optical surface, however, exhibited a large anisotropic optical response with a strong angular dependence following a sinusoidal behavior. Furthermore, we examined the spatial distribution of the reflection difference in Bi0.17Ca0.83MnO3+delta using infrared synchrotron radiation and could clearly distinguish microscopic anisotropic domains having different optical axes. These results demonstrate that our experimental scheme can be used as a powerful tool to spectrally and spatially resolve anisotropy of solid-state materials in the mid-infrared region.