The photoluminescence spectra of the 4-n-pentyl-4'-cyanobiphenyl (5CB) liquid crystal have been investigated in detail at low temperatures 4.2-200 K, for the first time. The spectral data obtained are compared to the results of the luminescence study for the 5CB nematic phase at T=300 K. The luminescence of the 5CB crystal state is characterized by emissions of both monomer and dimer structures. Besides, there are several energetically and conformationally non-equivalent types of monomers and dimers, and their amounts change with the temperature growth non-monotonously. The 503 several crystal modifications, having different 5CB monomer and dimer conformers, have been found out below T=10 K. The 5CB crystal-crystal transition at T=80 K is characterized with a total loss of the fine structure in the 5CB photoluminescence spectrum and a disappearance of the spectral band at 343 nm. At T=140 K, a new spectral band at 424 nm appears: it corresponds to the significantly overlapping 5CB dimers, its intensity grows under further heating. The present investigation gives a tool for the further characterization of the molecular alignments and changes in the 5CB molecular conformations, using the monomer and excimer fluorescence emissions as a probe. The conclusions made are confirmed by the IR-spectroscopy data, measured and analyzed for the 5CB in the same temperature region. (C) 2010 Elsevier B.V. All rights reserved.