The effect of volatile compounds from the mashed fresh, fallen, and dried leaves of Murraya exotica on the behavior of red imported fire ant (Solenopsis invicta, RIFA) workers was investigated by fumigation toxicity bioassay. The volatile compounds from different mashed leaves (fresh, fallen, and dried leaves) of M. exotica were collected by solid-phase microextraction and identified by gas chromatography–mass spectrometry. β-Caryophyllene, α-cedrene, α-copaene, β-cubebene, and germacrene D were identified as major components of the volatile compounds. In exposure time from 1 d to 9 d, the mortality of RIFA increased from 5.00% to 100.00% (fresh leaves), 11.67% to 93.33% (fallen leaves), and 15.00% to 83.33% (dried leaves) in minor workers, whereas in major workers, the increases were from 13.33% to 93.33% (fresh leaves), 6.67% to 83.33% (fallen leaves), and 10.00% to 60.00% (dried leaves). The volatile compounds reduced the walking and grasping abilities and aggregation rate of RIFA workers. Results indicate that mashed leaves of M. exotica have potential for controlling RIFA.