Scientific understanding of the molecular structure and adsorption of polymers at oil-water liquid interfaces is very limited. In this study the adsorption free energy at the oil (CCl4)-water interface was estimated using umbrella sampling molecular dynamics simulations for six carboxylate type vinyl polymers differing in hydrophobic nature and tacticity: isotactic and syndiotactic poly(acrylic acid) (i-PAA, s-PAA), isotactic and syndiotactic poly(methacrylic acid) (i-PMA, s-PMA), and atactic and syndiotactic poly(ethylacrylic acid) (a-PEA, s-PEA). ΔGads values are in the order i-PMA < a-PEA < s-PEA < s-PAA < i-PAA < s-PMA. The results show the significant and complex influence of the chemical nature as well as tacticity of the polymer on its adsorption free energy as related to hydrogen bonding and orientation of bonds with respect to oil and water phases. The influence of tacticity is found to be the highest for PMA, which is interpreted to occur due to the balance between interactions among side groups and those occurring between side groups and solvent. Interactions between side-groups are crucial for determining the conformation of PAA (most hydrophilic) and the solvation of the side-group in water is crucial for determining the conformation of PEA (most hydrophobic). The adsorption of PMA represents the transition between these two dominating effects. The molecular contributions to the enthalpy of adsorption indicate that adsorption is favored mainly through two interactions: polymer-CCl4 and water-water.