In this paper, we have described a simple and convenient method for the one-pot multicomponent reaction of aldehydes, malononitrile and thiols in the presence of a catalytic amount of Bronsted base potassium hydroxide for the efficient synthesis of highly functionalized pyridines. The notable features of this protocol are the simple experimental procedure, short reaction time, broad substrate scope and good yields using a catalytic amount of readily available and cheap base. The photophysical behaviours of the synthesized pyridines have been investigated by UV-Vis and fluorescence spectroscopy and some of the synthesized substituted pyridines exhibit promising fluorescence quantum yields.