In any laser skin treatment, the optical properties (absorption and scattering coefficients) are important parameters. The melanin content of skin influences the absorption of light in the skin. The spread in the values of the absorption coefficients for the South African skin phototypes are not known. A diffuse reflectance probe consisting of a ring of six light delivery fibers and a central collecting fiber was used to measure the diffused reflected light from the arms of 30 volunteers with skin phototypes I–V (on the Fitzpatrick scale). The absorption coefficient was calculated from these measurements. This real-time in vivo technique was used to determine the absorption coefficient of sun-exposed and -protected areas on the arm. The range of typical absorption coefficients for the South African skin phototypes is reported. The values for the darker South African skin types were much higher than was previously reported for darker skin phototypes. In the analysis, the contributions of the eumelanin and pheomelanin were separated, which resulted in improved curve fitting for volunteers of southern Asian ethnicity without compromising the other groups.