To get insight into the mechanism of the effect of room-temperature ionic liquids (RTILs) on the chemical vapor generation (CVG) of noble metals, gold was taken as a model element, and eight RTILs were examined. All the RTILs resulted in 3–24 times improvement in sensitivity for Au, depending on their nature. For the RTILs with identical anion, the RTILs with the cations of short chain exhibited better enhancement effect than those with long alkyl chain length or complex branch chain. For the RTILs with identical cation, the RTILs with Br− gave the best enhancement effect. The formation of ion pairs between the cation of RTILs and the anion species of gold via electrostatic interaction, and/or the substitution of the Cl− in the anion species of gold by the anion of RTILs likely enabled a more effective CVG reaction to occur. The RTILs also facilitated the generation of small bubbles and provided an electrostatic stabilization to protect the unstable volatile gold species and to help fast isolation of volatile gold species from the reaction mixture. 1-Butyl-3-methylimidazolium tetrafluoroborate [C4mim]Br gave the best improvement in the sensitivity (24 times) among the RTILs studied, and also reduced the interferences fromcommontransition and other noble metals. Based on the enhancement effect of [C4mim]Br, a novel flow injection–CVG–atomic fluorescence spectrometric method with a detection limit (3s) of 1.9 µgL−1 and a precision of 3.1% (50 µgL−1, RSD, n = 11) was developed for the determination of trace gold in geological samples.