Under normal viewing conditions, humans find it easy to distinguish between objects made out of different materials such as plastic, metal, or paper. Untextured materials such as these have different surface reflectance properties, including lightness and gloss. With single isolated images and unknown illumination conditions, the task of estimating surface reflectance is highly underconstrained, because many combinations of reflection and illumination are consistent with a given image. In order to work out how humans estimate surface reflectance properties, we asked subjects to match the appearance of isolated spheres taken out of their original contexts. We found that subjects were able to perform the task accurately and reliably without contextual information to specify the illumination. The spheres were rendered under a variety of artificial illuminations, such as a single point light source, and a number of photographically-captured real-world illuminations from both indoor and outdoor scenes. Subjects performed more accurately for stimuli viewed under real-world patterns of illumination than under artificial illuminations, suggesting that subjects use stored assumptions about the regularities of real-world illuminations to solve the ill-posed problem.