The in vivo reflectance spectra of Caucasian skin, coated with preparations containing sunscreen vehicle, vehicle with olive oil and vehicle with the UVB and UVA absorbers 2-ethylhexyl-4-methoxycinnamate and 4-t-butyl-4′-methoxydibenzoylmethane were determined. All preparations reduced the reflectance of skin throughout the UVA spectral range (320 to 400 nm), with the sunscreen preparations containing the UVB and UVB plus UVA absorbers reducing the reflectance more than the sunscreen vehicle alone. This phenomenon, which facilitates the penetration of UV radiation to the lower epidermis and dermal layers of skin and therefore lessens sunscreen efficacy, is attributed to optical coupling mediated by refractive index matching of the sunscreen to the upper epidermis. The greater reduction in skin diffuse reflectance caused by sunscreens containing methoxycinnamate is associated with this compound's high refractive index. Also, by determining the excitation spectra of the autofluorescence originating from the dermal layer of skin, the transmission spectra of the various components of sunscreen on skin were established, and these were in good general agreement with previously published spectra.