Pores of shale exhibit multiscale characteristics, and pore characterization is challenging due to the complexity of pore systems. Currently, research is focused on nano-submicron pores, but the structure of micrometer-scaled pores is not well understood. In this research, an investigation of the three-dimensional pore network of the Chang 7 shale in the Ordos Basin of China was conducted, in order to provide an insight into the full characteristics of pore systems. Nano-CT and micro-CT scanning technology was used to comprehensively delineate the pore structure at different scales, for further understanding the gas storage mechanism in shale rocks. Results show that the radius of micro-scale pores ranges from 1 to 15 μm, with an average of 2.8 μm, and pores with radii of 1–5 μm occupy approximately 90% of all the pores. For the nano-scale pores, the size ranges from 86 to 2679 nm, with an average of 152 nm, yet it has a rather concentrated distribution within 300 nm. The nano-scale pores constitute most of the pore amount in the shale, whereas the micro-scale pores constitute most of the pore volumes. Moreover, the results show that more than 70% of nano-scale pores in the Chang 7 shale are isolated pores, indicating that pore bodies formed in the shale reservoir have poor connectivity. Positive linear relationships between pore sizes and the number of pore throats at the micro-scale and nano-scale were both obtained, suggesting that larger pores tend to have better connectivity than smaller pores.