Porosity and permeability are key variables that link the thermal-hydrologic, geomechanical, and geochemical behavior in rock systems and are thus important input parameters for transport models. Neutron scattering studies indicate that the scales of pore sizes in rocks extend over many orders of magnitude from nanometer-sized pores with huge amounts of total surface area to large open fracture systems (multiscale porosity). However, despite considerable efforts combining conventional petrophysics, neutron scattering, and electron microscopy, the quantitative nature of this porosity in tight gas shales, especially at smaller scales and over larger rock volumes, remains largely unknown. Nor is it well understood how pore networks are affected by regional variation in rock composition and properties, thermal changes across the oil window (maturity), and, most critically, hydraulic fracturing. To improve this understanding, we have used a combination of small- and ultrasmall-angle neutron scattering (U)SANS with scanning electron microscope (SEM)/backscattered electron imaging to analyze the pore structure of clay- and carbonate-rich samples of the Eagle Ford Shale. This formation is hydrocarbon rich, straddles the oil window, and is one of the most actively drilled oil and gas targets in the United States. Several important trends in the Eagle Ford rock pore structure have been identified using our approach. The (U)SANS results reflected the connected (effective) and unconnected porosity, as well as the volume occupied by organic material. The latter could be separated using total organic carbon data and, at all maturities, constituted a significant fraction of the apparent porosity. At lower maturities, the pore structure was strongly anisotropic. However, this decreased with increasing maturity, eventually disappearing entirely for carbonate-rich samples. In clay- and carbonate-rich samples, a significant reduction in total porosity occurred at (U)SANS scales, much of it during initial increases in maturity. This apparently contradicted SEM observations that showed increases in intraorganic porosity with increasing maturity. Organic-rich shales are, however, a very complex material from the point of view of scattering studies, and a more detailed analysis is needed to better understand these observations.