The red imported fire ant, Solenopsis invicta, is a highly aggressive species with rapid dispersal speed, causing significant ecological impacts in invaded areas. Although many studies reported the impact of S. invicta on invertebrates, only a little attention has been paid to vertebrates, and a systematic review still needs to be provided. This paper aims to review the impact of S. invicta invasion on various taxa of vertebrates at individual and population levels. In addition, the physiological and behavioral defenses of vertebrates against S. invicta are discussed. Methods such as field surveys, case reports, laboratory evaluation, comparative analysis, and artificial removal of S. invicta in certain vertebrate habitats have been widely used to investigate the impact of S. invicta on vertebrates. In general, S. invicta usually attacks vertebrates by injecting venom with the stinger on the end of the abdomen. Therefore, S. invicta can directly prey on eggs, immatures, and adults of various vertebrates and negatively affect their behaviors. In addition, S. invicta can decrease the abundance of invertebrate species in the habitat and indirectly influence the population of vertebrate predators. Although S. invicta is a terrestrial animal, fish may be poisoned by consuming the winged S. invicta falling into the water and threated by S. invicta rafts that can float during flood. Because amphibians usually have relatively small body sizes and low mobility, and their skin lacks the protection of stratum corneum, scales and feathers, they are vulnerable to S. invicta attacks. For reptiles and birds, S. invicta usually preys on eggs and immature individuals and disturbs the reproductive behaviors of adults, decreasing their breeding success. In addition, S. invicta negatively affects foraging behaviors and the population of small mammals and causes enormous economic losses in animal industries due to its sting on domestic animals. A few vertebrates have behavioral strategies (e.g., kicking off fire ants with appendages or avoiding consuming or closing to S. invicta) to protect themselves from S. invicta attacking. Also, various physiological reactions (e.g., producing venom antibodies and adjusting hormone levels) can be observed in some vertebrates after S. invicta stinging. However, it is unclear whether such mechanisms are widespread in vertebrate animals and how they can protect vertebrates from S. invicta attacks. It is worth noting that almost all relative studies were conducted by foreign researchers. More attention should be paid to the potential impact of S. invicta on economic-important, endangered, or ant-feeding vertebrate species in China.