The incorporation of electron-withdrawing pyrimidine rings within π-extended systems allows access to a wide variety of fluorescent push-pull molecules that display emission properties highly sensitive to external stimuli. A suitable design of these compounds leads to interesting materials for a variety of optoelectronic applications. In this context, a vast number of arylvinylpyrimidine-based chromophores have been extensively studied during the last two decades. Along with the main synthetic pathways, this review summarizes the photophysical features of these active compounds having great potential and their most important applications as sensors and luminescence materials.