Charge-transfer (CT) complexes formed between Rhodamine 6G (Rh6G) as donor with iodine, CLA and PA as acceptors have been studied spectrophotometrically. The synthesis and characterization of Rhodamine 6G CT-complexes of iodine, [(Rh6G)₂]I⁺.I₃^ˉ, chloranilic acid (CLA), [(Rh6G)(CLA)] and picric acid (PA) [(Rh6G)(PA)] were described. These complexes are readily prepared from the reaction of Rh6G with I₂, CLA and PA with CHCl₃ solvent. Mid and far IR, ¹H-NMR, UV-Vis techniques, elemental analyses (CHN) and thermal studies, characterize the three new Rhodamine 6G charge-transfer complexes. Modified Benesi-Hildebrand method was applied to the determination of association constant and molar extinction coefficient.