In this work, the role of intermolecular interaction on the aggregation-induced emission (AIE) phenomenon and organic light-emitting diodes’ (OLEDs) performance was investigated. During the research, a group of compounds consisting of the (-CH=C(CN)(COOR)) moiety with identical energy parameters was designed using the DFT approach and successfully synthesized. The optical, electrochemical, and aggregation-induced emission properties were studied. The aggregation-induced emission of compounds has been studied in the mixture of MeCN (as a good solvent) and water (as a poor solvent) with different water fractions ranging from 0% to 99%. Moreover, the time dependence on the AIE feature was also evaluated. Thanks to their molecular structures, almost identical behavior of these substances in dilute solutions was observed. For molecules that exhibit the strong AIE phenomenon, emission efficiency increases rapidly during aggregation. What is also very interesting is it has been shown that by introducing an appropriate substituent, one can control the degree of intermolecular interactions and “control” the length of the emitted wave. Finally, OLEDs were fabricated by the spin-coating/evaporation hybrid method. Devices showed green–blueish electroluminescence (CIE coordinates: 0.107, 0.165) with maximum luminance reaching 25 cd m⁻² and EQE reaching 2%.