Hyperaccumulators are plant species that tolerate and accumulate very high concentrations of toxic metals, including Cd. Hyperaccumulation of heavy metals is reported to benefit plant biotic resistance; however, no prior study has examined the possible role of toxic metals on abiotic stress resistance in hyperaccumulators. A preliminary experiment found that Cd significantly improved plant growth of a hyperaccumulator, Sedum alfredii Hance, under heat stress. This study investigated the possible role of Cd in S. alfredii’s heat resistance, using infrared thermography, transmission electron microscopy (TEM), real-time quantitative polymerase chain reaction (RTqPCR), and high-throughput sequencing. The results showed that high temperatures irreversibly damaged stomatal function, chloroplast structure, photosynthesis in S. alfredii, and lowered survival rates to 25%. However, Cd application significantly decreased the leaf temperature of S. alfredii and increased the survival rate to 75%. Cd penetrated the guard cells, restored stomatal function, and mitigated excessive water loss from S. alfredii under heat stress. Moreover, it activated antioxidant enzymes, promoted phytohormone biosynthesis, and upregulated a series of unigenes, thereby augmenting heat resistance in S. alfredii. These results indicate that Cd effectively improved thermotolerance in S. alfredii by regulating stomatal movement and antioxidant systems via upregulation of phytohormones and heat shock proteins.