Synthetic access to a five (hetero)arene ring-fused 3-phenyl[1,2,4]triazines is described. The resulting compounds were characterized via 1H and 13C NMR, IR, UV–vis spectroscopy and HRMS. The structure of 3-phenyl[1,2,4]triazino[5,6-c]quinoline was unambiguously confirmed by single crystal XRD.