Herein we report an iron-catalyzed multicomponent dehydrogenative functionalization of alcohols to pyrimidines under atmospheric conditions. Using a well-defined Fe(II)-complex featuring redox noninnocent 2-phenylazo-(1,10-phenanthroline) ligand, as a catalyst, a wide array of 2,4,6-trisubstituted pyrimidines were prepared via dehydrogenative coupling of primary and secondary alcohols with amidines under air at 100 °C. A few control experiments were carried out to understand and unveil the plausible reaction mechanism. (Figure presented.).