Four novel liquid-crystalline azo-dyes bearing two amino-nitro substituted azobenzene units linked by a well-defined oligo(ethylene glycol) spacer (DIRED-PEG series): (E)-N,N'-(2,2'-oxybis(ethane-2,1-diyl))bis(N-methyl-4((E)-(4-nitrophenyl)diazenyl) benzenamine) (DIRED-PEG-2), (E)-N,N'-(2,2'(ethane-1,2-diylbis(oxy)) bis(ethane-2,1-diyl)) bis(N-methyl-4-((E)-(4-nitrophenyl) diazenyl) benzenamine) (DIRED-PEG-3), (E)-N,N'-(2,2'-(2,2'-oxybis (ethane-2,1-diyl) bis(oxy)) bis(ethane-2,1-diyl)) bis(N-methyl-4-((E)-(4-nitrophenyl) diazenyl) benzenamine) (DIRED-PEG-4) and N1,N17-dimethyl-N1,N17-bis (4-((E)-(4-nitrophenyl) diazenyl) phenyl)-3,6,9,12,15-pentaoxaheptadecane-1,17-diamine (DIRED-PEG-6) have been synthesized. These dyes were fully characterized by FTIR, (1)H and (13)C NMR spectroscopies, and their thermal and optical properties were studied. Besides, the liquid-crystalline behaviour of these compounds was monitored in function of the temperature by light polarized microscopy. Finally. Langmuir films were prepared with these dyes. (C) 2011 Elsevier B.V. All rights reserved.