ABSTRACT Diffuse reflectance is widely used for examining rough surfaced materials, samples abraded on substrates, powder, and reactions on powders. A variety of sampling methods are used for diffuse reflectance analysis. It is important to understand the theoretical constraints to correctly interpret the data for qualitative or quantitative applications. This article reviews the most commonly used theory of diffuse reflectance and discusses its limitations relative to the various sample handling methods used and the commercially available diffuse reflectance accessories.