This paper discusses pore characterization of organic-rich shales using 3D high-resolution imaging and a topological data analysis (TDA) framework. In particular, our focus is on persistent homology. Our data set contains four organic-rich shale samples (imaged at 10 nm3/voxel) and a Bentheimer sandstone as the anchor point for comparison. The analysis shows that pores larger than 12.4 nm have poor connectivity, and there is no evidence of a percolating path through any of the shale samples.