Slags and ashes generated in thermal waste treatment facilities require proper management. In line with the principles of the circular economy, new, more economical, and ecological possibilities for utilizing these substances are sought. These waste materials exhibit characteristics similar to rocks in many aspects. This study focuses on analyzing the similarities and differences between nine selected rocks and three samples of slags and ashes obtained from municipal waste incineration. The main research device used was a polarizing microscope, using reflected, transmitted, and fluorescent light. Additionally, low-pressure gas adsorption equipment, as well as helium and quasi-liquid pycnometers, were used for complementary analysis. The parameters analyzed mainly covered broadly defined petrographic properties of rocks and slags, with a particular emphasis on porosity, porous structure, and the spatial distribution of pores and fractures. The conducted analyses confirmed a significant similarity between slags and ashes and clastic sedimentary rocks such as sandstones and mudstones. The research results underscore the importance of petrographic microscopic studies for analyzing materials other than rocks. They also allow for exploring applications for slags and ashes in areas traditionally reserved for natural rock resources. The findings also indicate the necessity of using methods other than microscopic ones to describe the pore space of rocks. The lower measurement range of the optical microscope is limited to approximately 1 μm, covering only macropores. Other methods extend this characteristic to micro- and mesopores. Therefore, a combination of different methods is often employed to obtain a more comprehensive characterization of rock porosity.