A simple catalytic synthesis of luminescent pyrimidines from benzamidines and alcohols is reported. These one-pot, acceptor-less dehydrogenative coupling reactions are catalyzed by a ruthenium hydrido chloride complex (1), supported by a chelating P^N ligand (L1) bearing a benzannulated phenanthridine donor arm. The pyrimidines thus produced are emissive in solution, with photoluminescence quantum yields reaching 72%. Details of the catalytic synthesis and characterization of the pyrimidines in both solution and the solid state are reported, along with computational modeling of the emissive excited states of representative examples.