The constructional details and method of operation of an optical diffusiometer are described. The apparatus makes use of a Mach‐Zehnder‐type interferometer, which has not previously been employed for the study of diffusion in liquid systems. The apparatus has been developed for the study of liquid systems whose components are volatile organic solvents. For this purpose a diffusion cell of novel design has been constructed. The diffusiometer has been checked using the system sucrose‐water at 25°C and values of the diffusion coefficient found over six determinations are within 0.2% of the reported value. With volatile liquids, the accuracy claimed is only 1%, although duplicates usually agreed to within 0.5%.