Polyacrylamide (PAM) is a water-soluble polymer with strong cohesiveness and a strong water absorption capacity, and it has been widely used to modify soil structural stability. However, little information is available on the impact of PAM application on the aggregate-breaking process of purple soils in hilly areas of southwestern China. Therefore, the current study aimed to examine the influence of PAM application on the aggregate stability of purple soil in terms of different breakdown mechanisms at different hillslope locations. Three disruptive tests employing the Le Bissonnais method (FW, fast-wetting sieving; SW, slow-wetting sieving; and WS, wet-stirring sieving) were used to determine the mean weight diameter (MWD), geometric mean diameter (GMD), and mass fractal dimension (D) of the soil aggregates, and soil erodibility factor (K) was calculated as an index of soil anti-erodibility. Overall, the major aggregate-breaking mechanism for purple soils was the following: SW (differential swelling) > WS (mechanical breakdown) > FW (slaking). The content of water-stable aggregates (>0.25 mm) obviously rose after PAM application, with the most significant influences shown under FW. A significant difference in MWD was observed between PAM application and without polyacrylamide application (CK) under WS (p < 0.05). However, there was a significant difference in GMD between PAM and CK (p < 0.05) under FW and SW. In comparison with CK, D value in PAM under FW and SW was significantly reduced, mainly at the slope locations of 0 and 20 m. A descending order of FW, WS, and SW was found on the basis of K value at different slope locations. These findings contribute to improved understanding of proper application of soil amendments to control soil and water loss in purple soils.