The fading of dyed material by light has long been subject of investigation, yet surprisingly little is known of the fundamental photochemical reactions, because of mainly the complex nature of dye-fibre system. The effect of the chemical structure of dye on lightfastness has been mostly studied when there is substituents on the place satisfied Hammett rule. Therefore, in this investigation the effectiveness of chemical structures of Congo Red and Benzopurpurine 4B unsatisfied Hammett rule on dyeing property and lightfastness of cotton was studied. The results obtained from this study were as follows; 1. Highly polar solvents showed hypsochromic shift. 2. Adsorption isotherm curves of the two dyes were Freundlich type. And Congo Red showed good dyeing property in comparision with Benzopurpurine 4B. 3. The type of the FR curve of the two dyes was first-ordr curve. And the CF curves of the two dyes showed normal fading state during irradiation. 4. During irradiation, the Hue was changed on the part of yellowish. The Value was increasing and the Chroma was decreasing. 5. Benzopurpurine 4B showed good lightfastness in comparision with Congo Red.