Pyrimidine moiety has been of long standing interest in organic and medicinal chemistry as a critical substructure of many drugs and of many natural products.1 An extensive research on this highly versatile template led to the introduction of several drugs into the market such as the hypocholesterolemic agent rosuvastatin (Crestor) and the potent anticancer drug imatinib (Gleevec).2 In addition to a privileged scaffold being a key binding fragment toward their biological targets the pyrimidine motifs have been utilized as molecular probes for the study of chemical/biological interfaces.3 Despite their prominent importance in these research areas the synthetic strategies to various pyrimidine derivatives are limited in their scope and generality for the functionalization of densely substituted ones. As an effort to such goals, herein we present a cascade reaction method for carbon-carbon cross-coupling reaction between 3, 4-dihydropyrimidine-1H-2-thiones (DHPMs) and azoles with concomitant aromatization under Pd/Cu catalytic system to produce diverse 2-azolylpyrimides in a single step. The reaction proceeded efficiently with a wide range of DHPM substrates and azoles as coupling partners.