A series of p-nitro-p'-alkoxy(OR)-substituted (E,E,E)-1,6-diphenyl-1,3,5-hexatrienes (1a,R)Me;1b,R= Et;1c, R = n-Pr; 1d, R = n- Bu) were prepared. The absorption and fluorescence spectra in solution were almost independent of the alkoxy chain length. The absorption maximum showed only a small dependence on the solvent polarity, whereas the fluorescence maximum red-shifted largely as the polarity increased. The solid-state absorption and fluorescence spectra were red-shifted relative to those in low polar solvents and were clearly dependent on the alkoxy chain length. The fluorescence maxima for the crystals of 1b and 1d were observed at 635-650 nm, which were red-shifted by 40-50 nm relative to those for 1a and 1c. The Stokes shifts were all relatively small (3000-3500 cm(-1)). For all four compounds, the fluorescence decay curves in the solid state were able to be analyzed by single-exponential fitting to give the lifetimes of 1.1-1.3 ns. This indicates that the emission of 1a-d is not originated from an excimer or molecular aggregates, but from only one emitting monomeric species. The fluorescence quantum yields of 1a-d were considerably high compared with the values for organic solids, which is consistent with their monomeric origin of emission. Single-crystal X-ray structure analyses of 1a, 1c, and 1d showed that the crystal packing was dependent on the alkoxy chain length. The crystals of 1a and 1c had herringbone structure, whereas that of 1d had pi-stacked structure. Strong pi-pi interaction in the crystal of 1d would be the cause of the spectral red shifts relative to those for 1a and 1c. No observation of excimer fluorescence from crystal 1d can be attributed to the limited overlap between the pi-planes of the molecules due to its "slipped-parallel" structure.