A new approach for the synthesis of long alkyl chain length stationary phases for use in reversed-phase liquid chromatography is described. Poly(ethylene-co-acrylic acid) copolymers (i.e., (-CH2CH2-)x[CH2CH(CO2H)-]y) with different levels of acrylic acid were covalently bonded to silica via glycidoxypropyl or aminopropyl linkages. 13C cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopy was used to characterize the new reversed-phase materials. Aspects of shape selectivity were evaluated for six different columns with Standard Reference Material (SRM) 869a, Column Selectivity Test Mixture for Liquid Chromatography. Selectivity for isomer separations was enhanced for stationary phases prepared with poly(ethylene-co-acrylic acid) containing a mass fraction of 5% acrylic acid. The relationship between alkyl conformation and chromatographic properties was studied by 13C magic angle spinning (MAS) NMR measurements, and correlations were made with the composition of the polymer. Finally, the effectiveness of this phase is demonstrated by the separation of several beta-carotene isomers.