The crystal and molecular structures of α,ω-bis [4-(4′-hexyloxybenzylideneiminophenyl)]octane (6O.8.O6) and the homologue α,ω-bis [4-(4′-heptyloxybenzylideneiminophenyl)]octane (7O.8.O7) have been determined by direct methods at room temperature. The crystals of both compounds belong to the monoclinic system with space group P 21/a and two molecules per unit cell which are placed on centers of symmetry. For 6O.8.O6: a = 10.613(4), b = 8.7596(10), c = 22.149(7) Å, β = 100.02(2)°; for 7O.8.O7: a = 5.909(4), b = 7.412(3), c = 47.174(27) Å, β = 91.15(3)°. The structures were refined by full-matrix least-squares calculations against F to R = 0.078 for 4993/(3596 unique) collected reflections for 6O.8.O6 and to R = 0.077 for 1772/(1548 unique) reflections for 7O.8.O7.