Combining a Gas-Injection System (GIS) with the Focused Ion Beam (FIB) has a broad scope of applications in sample preparation such as protective layer deposition, increasing material sputtering rates, and reducing FIB-related artifacts. On the other hand, injecting certain specific gases during a Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) analysis can significantly increase element ionization probability and, therefore, improve the quality of 3D representation of a sample elemental structure. In this work, for the first time, the potential of GIS for enhancing secondary ion signals acquired using a TOF detector incorporated into a commercial Ga⁺ FIB-SEM (Focused Ion Beam combined with Scanning Electron Microscope) instrument is presented. The depth profiles of pure metals (thin films of Cu, Zr, Ag, and W with the thickness in the order of 100 nm) were acquired under ambient vacuum conditions as well as under an exposure to water and fluorine gases. The influence of supplementary gases on the ion yields and sputtering rates was studied. Simulations were performed to assess the local gas pressure at the location of FIB-TOF-SIMS analysis. The highest enhancement of ionization probability was achieved in the case of the Cu thin film (10 times during water vapor coinjection and 510 times when using a fluorine gas). Regarding the sputtering rates, the response of Zr to the effect of the gases was the strongest. Compared to standard background pressure measurements, this thin film was milled around 6 times faster under exposure to water vapor and over 2 times faster when fluorine gas was supplied.