Objective To study the effects of paraphenylenediamine (PPD) and linear alkylbenzene sulphonate (LAS) alone and in combination on the skin. Methods Forty-eight guinea pigs were divided equally into 4 groups and exposed to PPD (4 mg/kg), LAS (12 mg/kg) and PPD (4 mg/kg) plus LAS (12 mg/kg) for 30 days. The biochemical parameters such as acid phosphatase, gtutathione-s-transferase, glutathione peroxidase, glutathione, lipid peroxidation and histamine contents in exposed skin were estimated. The histopathological examination of the exposed skin was also carried out. Results The skin enzymes, lipid peroxidation, and histamine increased while glutathione decreased in skin. The simultaneously exposed group showed additive toxic effects. The histopathological examination showed severe hyperkeratosis, thickening of collagen fibres and vacuolisation of epidermal cells in PPD plus LAS exposed skin. Conclusion The findings of the present study suggest that simultaneous exposure to PPD and LAS has additive toxic effects.