The paper presents the results of optimizing the conditions for the chromatographic determination of 2,4-dichlorophenoxyacetic acid and deltamethrin for two capillary columns (Supelcosil LC-18, Kromasil C-18). The modes of individual chromatography of pesticides were selected. The use of the isocratic elution mode in the joint presence of 2,4-dichlorophenoxyacetic acid and deltamethrin was shown and experimentally proved to be invalid. Three options were proposed for the conditions of the gradient mode of the separate detection of analytes in a mixture.