Based on the distribution constants of biphenazate, obtained experimentally and also calculated from literature data on the solubility of biphenazate in water and organic solvents, as well as experimental data on the extraction of biphenazate from plant matrices by various extractants, we selected the optimal conditions for extracting biphenazate from apples and cucumbers. The conditions for the purification of the extracts were also selected. Acetonitrile in the presence of ammonium sulfate and hexane was used for extraction of the pesticide. Purification of extracts of plant materials was carried out by partitioning between hexane and water-acetonitrile mixture. The samples obtained after this treatment were pure enough to determine the residual amounts of biphenazate in them at the maximum residue level determined in Belarus and the countries of the European Union, or lower using widespread liquid chromatography with diode-array (ultraviolet) detection.