The interaction of two recently synthesized ligands, a: 5-(2-hydroxybenzylidene) -1,3-dimethylpyrimidine-2,4,6 (1H,3H,5H) - train and b: 5-(2-hydroxy-5- nitrobenzylidene)-1,3-dimethylpyrimidine-2,4,6 (1H,3H,5H)- train with π acceptor( iodine) have been studied spectrophotometrically in chloroform solution. The formation constants (Kf) of complexes were established by using a Benesi- Hildebrand equation and mole ratio data. Formation of the CT complexes with iodine was confirmed by NMR and IR spectroscopies.