A high percentage of high-ash fine slime materials can deteriorate flotation selectivity through surface covering. This covering of the surface is one of the issues that need to be addressed for efficient flotation processing of difficult-to-separate and high-ash coals. In this study, we investigated the depression effect of SPP on high-ash fine mud by flotation kinetic tests. We also revealed the mechanism of SPP depression of fine slime flotation and enhanced flotation selectivity of difficult-to-separate and high-ash coals by means of Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), and Atomic Force Microscopy (AFM) analyses. The results showed that under the best condition of SPP dosage, clean coal with 9.75% ash content and 76.76% yield was obtained. Compared to the blank group, the ash content of the clean coal decreased by 2.39%, while the yield was only reduced by 2.18% in the presence of SPP. The reason for this was that the addition of SPP enhanced the stripping and dispersion of the gangue from the coal particle surface. The result was a reduction in the cover of the coal grain surface and an increase in the hydrophobic sites on the coal surface, thereby depressing the non-selective flotation of the gangue and enhancing the adsorption of the collector on the coal surface. The ash content of the flotation concentrate decreased, but the yield remained almost unchanged, which was the main reason for the better performance of SPP as a depressant compared to conventional depressants.