A method for the fast measurement oi the diffusion coefficients oi both small and large molecules in thin capillaries is reported. The method relies on Taylor-Aris dispersion theory and uses standard instrumentation for capillary zone electrophoresis. With this equipment, which consists of thin capillaries (50 to 100 micrometers in inner diameter), an injection system, detector ports, and computer data acquisition, a sample plug is pumped through the capillary at known velocity and the peak dispersion coefficient (D*) is measured. With the experimentally measured values of D* and flow velocity, and knowledge oi the inner diameter df the capillary, the molecular diffusion coefficient (D) can be rapidly derived. For example, for ovalbumin a D value of 0.759 x 10(-6) square centimeter per second is found versus a tabulated value of 0.776 x 10(-6) square centimeter per second (error, 2 percent). For hemoglobin a D value of 0.676 x 10(-6) square centimeter per second is obtained versus a literature value of 0.690 x 10(-6) square centimeter per second (error, 1.5 percent).