The surface and interfacial properties of the layered double hydroxide (LDH) phase Mg6Al2(OH)16CO3·4H2O (LDHCO3) and its nanocomposites with poly(styrenesulfonate) (LDHPSS) and poly(vinylsulfonate) (LDHPVS) were characterized by X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, transmission electron microscopy, He pycnometry, and electrophoretic light scattering. Polymer incorporation within the inter-gallery space resulted in a shift of the d003 reflection from 7.7 Å (LDHCO3) to 12.7 Å (LDHPVS) and 21 Å (LDHPSS). This increase in basal plane spacing caused the density of the LDH samples to decrease from 2.05 g/cm3 (LDHCO3) to 1.83 and 1.41 g/cm3 for LDHPVS and LDHPSS nanocomposites, respectively. LDHCO3 exhibited a positive electrophoretic mobility over the pH range from 4–11 with an isoelectric point (iep) at pH 11. However, the LDH nanocomposites displayed a negative electrophoretic mobility over the measured pH range, indicating that the surface properties of the LDH nanocomposites were dominated by negatively charged sulfonate groups from adsorbed polymer molecules.