The molecular structure of 1-phenyl-3-{4-[4-(4-octyloxybenzoyloxy)-phenyloxycarbonyl]phenyl}triazene-1-oxide, a member of newly developed liquid crystalline homologous series, has been investigated by crystal X-ray crystallography at low temperature (100 K). The title compound crystallizes in the triclinic crystal class in the space group P (1) over bar with cell parameters a = 5.766(5) angstrom, b = 12.151(10) angstrom, c = 21.751(17) angstrom, alpha = 79.089(13)degrees, beta = 88.646(14)degrees, gamma = 84.278(14)degrees, V 1489(2) angstrom(3) for Z = 2. It establishes the N-oxide form of the triazene-1-oxide moiety. The overall molecule is not planar, the dihedral angles between pairs of adjacent benzene rings are 14.00 (10), 52.36 (07), and 50.57 (07)degrees. Intramolecular N-H center dot center dot center dot O hydrogen-bonding is present within the triazene-1-oxide moiety of the title compound. The compound forms inversion dimer via an intermolecular N-H center dot center dot center dot O and an intermolecular C-H center dot center dot center dot O links. The dimers are then linked into chains in a parallel fashion by C-H center dot center dot center dot O hydrogen bonds. The crystal packing is further stabilized by C-H center dot center dot center dot pi interactions.