The infrared, Raman, and near ultraviolet spectra of selenophen have been measured. The vibrational spectra are consistent with the hypothesis of a planar structure for selenophen, a conclusion in contrast to that of previous investigations by Milazzo and co-workers. The 21 fundamentals are assigned to the irreducible representations of symmetry group C2v, on the basis of Raman intensities and polarisations, band contours in the infrared vapour spectrum, and activation in the liquid and solid infrared spectrum of A2-frequencies. The assignments to the approximate normal modes were made by analogy with those of thiophen. The near ultraviolet spectrum shows composite continuous absorption in the range 37,000–47,500 cm.–1. No traces of narrow peaks previously reported by Milazzo et al. in this spectral region were observed. The diffuse vibronic bands superposed to a continuum in the region 47,500–51,300 cm.–1 are interpreted on the basis of 405, 635, 1150, and perhaps 1350 cm.–1 excited-state totally symmetric vibrational frequencies with their origin at 47,800 cm.–1 This assignment is in disagreement with that proposed by Milazzo and co-workers.