A new charge transfer (CT) complex benzimidazolium-4-methyl benzenesulfonate formed between benzimidazole and 4-methyl benzenesulfonic acid has been studied spectrophotometrically in methanol at room temperature. The binding of the novel CT complex with calf thymus DNA has been investigated by adsorption spectrum, the establish the ability of the CT complex for its interaction with the chosen DNA. The elemental stiochiometry and the X-ray crystallographic structure of the complex were studied, showing the significance of sulfonate anion in holding stability. Powder XRD confirms the crystalline nature of the compound. NMR signals explicitly confirmed the molecular structure crystal. Antioxidant activity of the CT complex was found to be potent. TG-DTA studies also proves the stability of the synthesized complex.