This paper investigated the effect of Pr₆O11 addition on the acid resistance of ceramic proppant. Acid resistance of proppants can be improved by introducing Pr₆O11 into the Al₂O₃-CaO-MgO-SiO₂ (ACMS) system. To illustrate and explain the mechanism of acid resistance, the samples were characterized by different techniques, using X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The phase structure of the specimens was characterized by XRD and SEM-detected microstructures of the specimens. It was observed that with the increase of rare-earth oxide content, the acid solubility of the specimens decreased, and then increased when it reached the minimum value 0.45 wt %. The results of the research show that the improvement of acid resistance with rare-earth oxides was achieved by refining the grain size, strengthening the grain boundary, and turning Ca₂Al₂SiO₇, in which acid resistance is poor, into CaAl12O19, which possesses better acid resistance, and then enhance the acid resistance of the proppants. Furthermore, Pr₆O11 can form a solid solution with Ca₂Al₂SiO₇ and CaAl12O19. The acid resistance of CaAl12O19 improves with the increase of solid solubility. In contrast, the acid resistance of Ca₂Al₂SiO₇ will decrease after Ca₂Al₂SiO₇ forms a solid solution with Pr₆O11.