Understanding the conditions that promote the adsorption, assembly, and accumulation of charged macromolecules at the interface between aqueous and hydrophobic liquids is important to a multitude of biological, environmental, and industrial processes. Here, the oil-water interfacial behavior of stereoisomers of polymethacrylic acid (PMA), a model system for both naturally occurring and synthetic polyelectrolytes, is investigated with a combination of vibrational sum-frequency (VSF) spectroscopy, surface tension, and computations. Syndiotactic and isotactic isomers both show rapid adsorption to the oil-water interface with a net orientation indicative of a high degree of ordering. The stereoconfiguration is found to affect whether only a single layer or multiple layers assemble at the interface. Surface tension measurements show additional adsorption for syndiotactic PMA over time. The additional layers do not contribute to the VSF spectrum indicating disorder in all but the initial layer. The isotactic isomer shows no evidence of accumulation at the interface beyond the single ordered layer. Molecular dynamics calculations show marked differences between the two isomers in the orientation of their substituent groups at the interface. The hydrophilic and hydrophobic moieties in the isotactic isomer are easily partitioned to the water and oil phases, respectively, whereas a fair portion of hydrophobic groups remain in the water phase for the syndiotactic PMA. The available hydrophobic contacts in the water phase at the interface are credited with allowing further adsorption.