An HPLC technique for the size determination of colloidal cadmium sulphide and zinc sulphide in a diameter range from 20 down to 2 nm using silica with pore sizes from 30 to 100 nm is described. The growth of the particles during the run was suppressed by the addition of stabilizers to the eluent and by the use of reversed-phase silica as the stationary phase for inorganic stabilizers. The calibration of the column sets by electron microscopy resulted in a linear relationship between the logarithm of the particle diameter and the elution time. The analysis was carried out within 4–10 min. The lateral resolution lay between 1.3% for larger particles and 1.9% for smaller particles. Below a diameter of 13 nm these values were better than those found from electron microscopy. From the comparison of the calibration lines for various colloidal materials, the differences in their electrical double layers could be estimated. The limitations of the method are discussed and the size-exclusion chromatographic and electron microscopic methods are compared.