We have developed a system to measure both the optical properties of facial skin and the three-dimensional shape of the face. To measure the three-dimensional facial shape, our system uses a light-field camera to provide a focused image and a depth image simultaneously. The light source uses a projector that produces a high-frequency binary illumination pattern to separate the subsurface scattering and surface reflections from the facial skin. Using a dichromatic reflection model, the surface reflection image of the skin can be separated further into a specular reflection component and a diffuse reflection component. Verification using physically controlled objects showed that the separation of the optical properties by the system correlated with the subsurface scattering, specular reflection, or diffuse reflection characteristics of each object. The method presented here opens new possibilities in cosmetology and skin pharmacology for measurement of the skin’s gloss and absorption kinetics and the pharmacodynamics of various external agents.