Resonant x-ray diffraction was carried out at the Se K edge in thick free-standing films of a selenophene liquid crystalline material, revealing detail of the structure of the ferro-, ferri-, and antiferroelectric phases. The ferrielectric phase was shown to have a three-layer superlattice. Moreover, the structure of a lower temperature hexatic phase was established. For the antiferroelectric phase, investigations were also carried out in a planar device configuration. The device allowed resonant scattering experiments to be carried out with and without the application of an electric field and resonant data are compared with electro-optic measurements carried out on the same device.