Organic/Inorganic hybrid silicone polymers are widely used in cosmetics, inks, paints and in fabric care applications. Some of these current industrial applications, such as the treatment of fibers to impart 'bounciness' to fabrics, are based on the speculation that the siloxane backbone (-O-Si-O-) adopts a helical conformation when adsorbed at the interface. While such helical conformations are hypothesized for poly(dimethylsiloxanes) (PDMS) in past, the effect of grafting functional hydrophilic side chains to the polymer backbone on the interfacial conformation and the resulting interfacial properties is unknown. The addition of hydrophilic grafts can provide molecular anchors to optimize the interfacial contact for a particular application, and hence it is very important to investigate experimentally and theoretically the effect of such modifications. Experimentally, Langmuir isotherms were measured for PDMS and siloxanes with different hydrophilic grafted side chains (amino, quarternized amino and carboxylic). The isotherms indicate that the conformations of the chains depend on the available area at the interface, with conformational transitions at specific surface concentrations. For PDMS adsorbed at the air/water interface, a first order phase transition was observed upon compression. The polymer chains assemble from a disordered stretched phase into a phase in which the individual chains adopt a coiled conformation. Such transition was not observed when the PDMS chains were modified with hydrophilic side groups. The loss in the transition was attributed to the strong interaction of the hydrophilic groups with the water subphase, which prevented the coiling of the backbone at the interface since this coiling requires some of the side chains to be removed from the water subphase. However, the strong interaction gives rise to a larger Gibbs surface elasticity of the monolayer, as the side chain-water interaction resists further polymer compression. Therefore, the behavior of modified polymer is determined by competition of two simultaneous phenomena – compression of the modified silicone chains and the conformational change. Molecular simulation studies were utilized to understand these hydrophilic side chain/water-subphase interactions. Depth profile and binding energy data were analyzed to develop a molecular level understanding. The silicone backbone interaction with water was observed to be primarily van der Waals kind interaction, whereas the functional groups interact mostly through electrostatic interactions. It was observed that among the functional polymers, the ones with higher hydrophilicity interact more strongly with the water molecules. This stronger interaction leads the hydrophilic polymer molecules to penetrate deeper into the water surface than the hydrophobic PDMS chain, preventing the coil configuration and giving rise to a greater surface elasticity. Such information can be useful in tailoring polymers for specific applications by controlling their degree of functionalization, the type of side groups to use and the appropriate concentration required.