In this work, a three-stage and easily scalable synthesis of 2,6-dicyano-4-pyrone (overall yield of 45%) as a new convenient building block has been developed from diethyl acetonedioxalate. It was shown that the transformation with hydroxylamine and [3 + 2]-cycloaddition, in contrast to the reactions with hydrazines, selectively proceed through the attack at the cyano groups without the pyrone ring-opening to give symmetrical and unsymmetrical pyrone-bearing heterocyclic triads containing 1,2,4- and 1,3,4-oxadiazoles as well as tetrazole moieties. The reaction of 2,6-bis­(hetaryl)-4-pyrones with ammonia afforded 2,6-bis­(hetaryl)­pyridines in 63–87% yields. The 4-pyridone/4-pyridinol tautomerism of 2,6-bis­(hetaryl)­pyridinols and the influence of the nature of adjacent azolyl moieties on this equilibrium have been discussed.