A facile one-step approach towards 3-cyano-2-azaanthracenes via the [4+2] cycloaddition reaction between 5-cyano-1,2,4-triazines and 2,3-dehydronaphthalene, generated in situ from commercially available 3-amino-2-naphthoic acid, has been reported. The influence of the 1,2,4-triazine ring sub- stituents nature on the product yield has been studied. The observed experimental results were con- firmed by DFT calculations of the HOMO-LUMO energy levels of the both cycloaddends. The photophysical properties of the products have been investigated.