Described is a method for determining a dwell volume of a liquid chromatography system and a liquid chromatography system that can determined the system dwell volume. The method includes mixing a flow of a first solvent with a flow of a second solvent to form a solvent mixture. The flows of the first and second solvents are decreased and increased, respectively, to generate a gradient composition. A system pressure of the liquid chromatography system is measured to determine a pressure trace defined as the measured system pressure as a function of time. The dwell volume of the system is determined from a time delay determined between the gradient composition at the mixing location and the pressure trace. The method can be performed with a liquid chromatography system having a chromatographic column or a flow restrictor used in place of the chromatographic column.