Polymer collapse, which occurs in conjunction with preferential adsorption of amphiphilic cosolvents, can also be driven by changes in the interface formation free energy originating from repulsive polymer-(co)solvent interactions (solvent-excluded-volume interactions) via a surfactant-like mechanism. We observe that the free energy corresponding to the formation of both coil- (ΔG^C_Excl–Vol) and globule-sized cavities (ΔG^G _Excl–Vol) (repulsive polymer-solvent interface) monotonically decreases with increase in the alcohol concentration with a faster decrease for the globule-size cavity. This is due to the surfactant-like behavior of amphiphilic cosolvents such as alcohols which screen the hydrophobic polymer-water interface and reduce the unfavorable polymer-water interactions by preferentially adsorbing on the polymer surface. These results correlate with the trends in the surface tension of water-alcohol solutions, indicating that a macroscopic thermodynamic description applies in macromolecular solvation. The extent of preferential adsorption of the cosolvent is dependent on the interplay between the extent of screening and the loss of cosolvent translational entropy in the bulk (due to preferential accumulation). At low alcohol concentrations, the cosolvent can screen the surface of the globule state more effectively than the coil state due to the compact shape and smaller solvent accessible surface area (SASA) of the former. This leads to a higher preferential adsorption of the cosolvent on the globule state in comparison to the coil state which in turn causes ΔG^G _Excl–Vol to decrease faster than ΔG^C_Excl–Vol thereby shifting the coil-globule equilibrium towards the globule state. Our results also show that both ΔG^G _Excl–Vol and ΔG^C _Excl–Vol decrease faster with alcohol concentration in water-ethanol solutions in comparison to water-methanol solutions. This occurs because, at the same alcohol concentration, ethanol screens the hydrophobic polymer interface more effectively than methanol due to its larger size. These trends correlate with the observation that the surface tension of alcohol-water mixtures decreases at a higher rate for higher alcohols. This surfactant-like mechanism is able to rationalize the experimentally observed changes in lower critical solution temperature (LCST) behavior of higher molecular weight polymers and changes in LCST behavior in aqueous solutions with higher alcohols. Given that this mechanism is not dependent on the specific attractive interactions, it is generic and applicable to wide variety of macromolecular systems.