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Polyurethane foams (PUF) are of great interest in analytical chemistry of organic substances. The main advantages of these sorbents are: high effectiveness, universality, chemical and mechanical stability, sustainability in organic solvents, availability and relatively low cost. The unique sorption properties of these synthetic polymeric materials are mainly due to the combination of different hydrophilic and hydrophobic active centers and reactive terminal groups. The paper summarizes the results of investigations of sorption and chemosorption on PUF of different organic substances: polycyclic aromatic hydrocarbons, cationic and anionic surfactants, phenols, hydroxybenzoic acids and their azo-derivatives, sulfophthalein and xanthene dyes. General factors influencing on the sorption have been revealed; relations between the sorption parameters and physicochemical properties of the sorbent and sorbate have been established. A classification of the sorption systems with participation of PUF based on conception of different sorbent-sorbate intermolecular interactions has been suggested. The ways of preconcentration of organic substances have been developed. They have given rise to the hybrid and combined analytical techniques. It has been shown that due to rational choice of volume of the sample, mass of the sorbent, using sequential sorption, one can achieve enrichment factors up to 104. The substances can be determined directly in matrix of the sorbent by diffuse reflectance spectroscopy, luminescence and colorimetry. The examples showing advantages of such sorption-spectroscopy analytical techniques have been given for polyaromatic hydrocarbons, phenols and ionogenic surfactants.