This study gives valuable insights into the microstructure and pore space characteristics of 17 compositionally variable Visean shale samples from the Ukrainian Dniepr-Donets Basin (the ‘Rudov Beds’). The representative imaging area varies considerably (from 10 000 to >300 000 μm2) as a function of the mineralogy and diagenetic overprinting. The pores hosted in organic matter (OM) are restricted to secondary solid bitumen. Based on high-resolution maps from broad ion beam scanning electron microscopy combined with organic geochemical and bulk mineralogical data, we propose that the amount of OM-hosted porosity responds to the availability of pore space, enabling the accumulation of an early oil phase, which is then progressively transformed to a porous solid bitumen residue. The type of OM porosity (pendular/interface v. spongy) is reflected in the individual pore size distributions: The spongy pores are usually smaller (<50 nm) than the pendular or OM–mineral interface pores. The OM-hosted porosity coincides with differences in the composition of the extract, with high amounts of extractable OM and saturated/aromatic compound ratios indicative of abundant porous solid bitumen. The average circularity and aspect ratio of the mineral matrix pores correlate with the corresponding values for the OM-hosted pores, which show a preferred bedding-parallel orientation, suggesting that compaction influenced both types of pore.