Mudstones exert a fundamental control on the flow of both aqueous and nonaqueous fluids in sedimentary basins. Predicting their flow and storage properties requires an understanding of pore size and connectivity, yet there are very few quantitative descriptions of pore systems of mineralogically and texturally well-characterized mudstones. We use a combination of electron microscopy, mercury injection capillary pressure porosimetry, and CO 2 sorption methods to generate a quantitative description of the size distribution, connectivity, and evolution of pore systems in a sequence of Posidonia Shale mudstones buried to 100-180°C. We place the pore data into a detailed mineralogical, petrographical, and textural context to show that the nature and evolution of porosity and pore systems can be described in terms of associations with clay-rich, microfossil-rich, and organic matter-rich domains, common to many mudstones. Pore size distributions are described by power laws, and pore systems are well connected across the full nanometermicrometer spectrum of pore sizes. However, connected networks occur primarily through pores <10 nm radius, with typically 20-40% of total porosity associated with pores with radii <~3 nm, within both organic matter and the clay matrix. Clay-rich, microfossil-rich, and organic matter-rich domains have distinct pore size distributions which evolve in very different ways with increasing thermal maturity. We suggest that the flow of aqueous and nonaqueous fluids depends not only on the overall connectivity of pores but also the larger-scale connectivity and wetting state of clay-rich, microfossil-rich, and organic matter-rich domains.Plain Language Summary Mudstones are Cinderella sediments: important but neglected. The most abundant sediment type, they act as unconventional oil and gas reservoirs, as top seals to conventional hydrocarbon reservoirs, and as critical barriers to the leakage of CO 2 and radionuclides from underground storage sites. Risking and predicting flow and leakage through these rocks requires a quantitative description of pore systems and their connectivity. This is challenging since even the biggest pores in shales are smaller than a micron, with many pores only a few nanometers in size. Our work uses a combination of techniques to characterize and quantify the nanoporous nature of shales. Pores are generally smaller than 100 nm but are well connected, but mainly through throats less than 20 nm. We have also placed the pore system data into a geological framework in order to be more predictive about the pore systems of shales generally. By quantifying the nature of pores in the various mineral and organic building blocks of shales we can consider the larger scale flow properties of shales and thus their potential either to transmit fluid (useful for a shale gas reservoir) or to retain fluid (useful for a CO 2 or nuclear waste storage site).Quantitative descriptions of pore systems underpin our understanding of the storage and flow of both aqueous and nonaqueous fluids in...