Simple Summary: The red imported fire ant is an invasive pest worldwide and a social insect that presents a significant risk to agricultural productivity, ecosystems, and human health. This work presents the selection of three nanomaterials out of a total of 16 species. We assessed the toxicity and behavioral alteration effects of these three materials individually, as well as in combination with indoxacarb, on red imported fire ants. The results showed that diatomite and multi-walled carbon nanotubes could enhance the activity of indoxacarb against red imported fire ants and inhibit their colony behavior. Diatomite and multi-walled carbon nanotubes can be added as pesticide additives to improve the control effects on red imported fire ants, reduce the use of indoxacarb, and delay the development of resistance. The red imported fire ant (Solenopsis invicta Buren) is one of the 100 worst invasive alien species in the world. At present, the control of red imported fire ants is still mainly based on chemical control, and the most commonly used is indoxacarb bait. In this study, the contact and feeding toxicity of 16 kinds of nanomaterials to workers, larvae, and reproductive ants were evaluated after 24 h, 48 h, and 72 h. The results showed that the mortality of diatomite, Silica (raspberry-shaped), and multi-walled carbon nanotubes among workers reached 98.67%, 97.33%, and 68%, respectively, after contact treatment of 72 h. The mortality of both larval and reproductive ants was less than 20% after 72 h of treatment. All mortality rates in the fed treatment group were below 20% after 72 h. Subsequently, we evaluated the digging, corpse-removal, and foraging behaviors of workers after feeding with diatomite, Silica (raspberry-shaped), and multi-walled carbon nanotubes for 24 h, which yielded inhibitory effects on the behavior of red imported fire ants. The most effective was diatomite, which dramatically decreased the number of workers that dug, extended the time needed for worker ant corpse removal and foraging activities, decreased the number of workers that foraged, and decreased the weight of the food carried by the workers. In addition, we also evaluated the contact and feeding toxicity of these three nanomaterials in combination with indoxacarb on red imported fire ants. According to contact toxicity, after 12 h of contact treatment, the death rate among the red imported fire ants exposed to the three materials combined with indoxacarb reached more than 97%. After 72 h of exposure treatment, the mortality rate of larvae was more than 73% when the nanomaterial content was above 1% and 83% when the diatomite content was 0.5%, which was significantly higher than the 50% recorded in the indoxacarb control group. After 72 h of feeding treatment, the mortality of diatomite, Silica (raspberry-shaped), and multi-walled carbon nanotubes combined with indoxacarb reached 92%, 87%, and 98%, respectively. The death rates of the three kinds of composite ants reached 97%, 67%, and 87%, respectively. The three kinds of composite food had significant inhibitory effects on the behavior of workers, and the trend was largely consistent with the effect of nanomaterials alone. This study provides technical support for the application of nanomaterials in red imported fire ant control. [ABSTRACT FROM AUTHOR]