The one-step preparation of diethyl 2-ethoxy-6-CF3-2H-pyran-3,5-dicarboxylate via the condensation of ethyl 4,4,4-trifluoroacetoacetate with CH(OEt)3 has been reported and a plausible mechanism for this transformation is discussed. To demonstrate the synthetic potential of the obtained pyran, the reactions with ammonia and aromatic amines to give trifluoromethylated pyridine derivatives are presented.