The work reports synthesis of twelve novel ethyl 4-(6-substituted-4-oxo-4H-chromen-3-yl)-6-methyl-2-thioxo/oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate derivatives 4(a-f) and 4-(6-substituted-4-oxo-4H-chromen-3-yl)-6-methyl-2- thioxo/oxo-1,2,3,4-tetrahydropyrimidine-5-carbohydrazide derivatives 6(a-f). The novel chromone-pyrimidine coupled derivatives were synthesized under solvent-free condition using Triethyl ammonium sulphate [Et₃NH][HSO₄] as an efficient, eco-friendly and reusable catalyst.  Compared to other methods, this new method consistently has advantages, including excellent yields, a short reaction time, mild reaction conditions and catalyst reusability. The heterocyclic compound Chromone, is associated with diverse biological activities of immense importance. The nitrogen containing heterocycle such as pyrimidine has attracted continuing interest because of its varied biological activities and its occurrence in natural medicinal plants.  Pyrimidine and its derivatives are used as antifungal agents, antibacterial agents, anticancer agents, etc. Considering the importance of the two pharmacophores, promoted us to club both the pharmacophores in a single molecule using green protocol. The structures of the synthesized compounds were confirmed by spectral characterization such as IR, ¹H NMR, ¹³CNMR and Mass spectral studies.