A series of online interactive teaching units have been developed that illustrate the use of experimentally measured three-dimensional (3D) structures to teach fundamental chemistry concepts. The units integrate a 500-structure subset of the Cambridge Structural Database specially chosen for their pedagogical value. The units span a number of key chemical concepts (aromaticity, ring strain and conformation, stereochemistry and chirality, VSEPR, and hapticity) and guide students via a Web-based interface to visualize and interact with a diverse range of molecules. The units were designed to help students develop a visual understanding of 3D chemical structure and gain an appreciation of the unique advantages afforded by working with experimentally measured data. (Contains 10 figures and 1 table.)