There is currently a growing interest in imino derivatives of compounds such as thiadiazoles and other groups of compounds whose extended π-electron systems enhance their photophysical properties. These compounds also show low toxicity and strong antifungal activity, making them effective against fungal pathogens in crops. For the above reasons, in the first part of the paper, the structure of the selected analogs was considered, and detailed spectroscopic analyses were conducted focusing on the excited state intramolecular proton transfer (ESIPT) process taking place in the same. Measurements were taken in terms of absorption spectroscopy and electron fluorescence, synchronous spectra, and fluorescence lifetimes, as well as calculations of fluorescence quantum efficiency in selected solvents and concentrations. In the spectral observations, the ESIPT process was manifested in several solvents as very distinct dual fluorescence. Moreover, in selected molecules, this phenomenon was strongly related to molecular aggregation, which was associated with not very efficient but nonetheless visible fluorescence of the AIE (Aggregation-Induced Emission) type. In the second part of the paper, a detailed preliminary study is presented exploring the microbiological properties of selected imino-1,3,4-thiadiazole derivatives in the context of their potential applicability as inhibitors affecting the development and growth of some of the most important fungal pathogens attacking cereal crops and posing an increasing threat to modern agriculture. Overall, the research presented in this article provides a detailed, experimental analysis of the spectroscopic properties of selected imino-thiadiazoles and points to their potential use as novel and effective solutions capable of limiting the growth and development of fungal pathogens in cereals.