Fluorescent organic dyes play an essential role in the creation of new "smart" materials. Fragments and functional groups capable of free rotation around single bonds can significantly change the fluorescent organic dye's electronic structure under analyte effects, phase state transitions, or changes in temperature, pressure, and media polarity. Dependencies between steric and electronic structures become highly important in transition from a solution to a solid-state. Such transitions are accompanied by a significant increase in the dye molecular structure's rigidity due to supramolecular associates' formation such as H-bonding, π···π and dipole–dipole interactions. Among those supramolecular effects, H-bonding interactions, first of all, lead to significant molecular packing changes between loose or rigid structures, thus affecting the fluorescent dye's electronic states' energy and configuration, its fluorescent signal's position and intensity. All the functional groups and heteroatoms that are met in the organic dyes seem to be involved in the control of fluorescence via H-bonding: C-H···N, C-H···π, S = O···H-C, P = O···H, C-H···O, NH···N, C − H···C, C − H···Se, N–H···O, C − H···F, C-F···H. Effects of molecular packing of fluorescent organic dyes are successfully used in developing mechano-, piezo-, thermo- fluorochromes materials for their applications in the optical recording of information, sensors, security items, memory elements, organic light-emitting diodes (OLEDs) technologies.