Block and random copolymers of butadiene and styrene as well as polybutadiene and polystyrene homopolymers have been investigated with respect to their monolayer properties and photooxidation behavior. Whereas polystyrene and block copolymers of styrene and butadiene form stable monolayers, polybutadienes and random copolymers do not interact with the aqueous subphase. The monolayer properties of block copolymers with different styrene content indicate that polybutadiene also contributes to the surface pressure. Photo-oxidation of random and block copolymers of styrene and butadiene leads to a significant enhancement in surface pressure of the monolayers due to the generation of groups which can effectively interact with the aqueous surface. FTIR spectral studies show the formation of carbonyl, hydroxyl, and hydroperoxyl groups in the polymers on photooxidation. A comparison of the pressure-area isotherms of random and block copolymers oxidized in solution indicates that there is an energy transfer from butadiene to styrene units in the case of random copolymers, resulting in a protective effect of butadiene units from oxidation. In addition, in the monolayers of oxidized block copolymers, a phase transition occurs which is attributed to the extrusion of polystyrene blocks from the monolayer. The surface pressure-area isotherms and the rates of photooxidation are strongly dependent on the microstructure of polybutadiene as well as on whether oxidation is performed in solution or at the oxygen-water interface.