Alongside volcanic eruptions in the middle and late Permian, the sedimentary environment and process changed, and the lithofacies characteristics varied conspicuously in the marine deposits of the Sichuan Basin (China). The tuffaceous rocks, as a new type of unconventional reservoir, provide strong evidence for marine and volcanic influences on the lithology and reservoir potential of the rocks. With experimental studies relying on field outcrops, thin sections, scanning electron microscopy and whole-rock X-ray diffraction (XRD), the researchers analyzed the lithofacies characteristics, pore types and controlling factors on the various types of pores in the tuffaceous rocks. We identified three lithofacies types in this new type of Permian reservoir in the Sichuan Basin, namely tuff, sedimentary tuff, and tuffaceous mudstone. The mineral composition of the three lithofacies includes quartz, feldspar, carbonate minerals, pyrite, and clay, among which feldspar is mainly potassium feldspar. Tuff has high tuff content, and the lowest clay and TOC content; tuffaceous mudstones have the highest clay and TOC content, and the lowest tuff content. The pore types of the tuffaceous rocks are mainly nano-scale shrinkage pores, with a small number of intergranular pores including intragranular pores, intergranular pores, and organic pores. The shrinkage pores account for 81.9% of the total pores, and organic pores account for 11.2% of the total pores. In the tuffaceous rocks, the tuff content, quartz and feldspar content, and pyrite content are inversely correlated with porosity, while the clay content and TOC content are positively correlated with porosity. The porosity of tuff is the lowest, followed by sedimentary tuff, and the porosity of tuffaceous mudstone is the highest. Tuffaceous rocks form many micropores in the process of devitrification. Organic matter pyrolysis and organic acid dissolution also increase the reservoir space and porosity of the reservoir. This new type of reservoir has the ability of hydrocarbon accumulation along with the reservoir performance, and thus it has greater exploration prospects.