Double-pulse laser-induced breakdown spectroscopy (DP-LIBS) has been shown to enhance LIBS spectra. Several researchers have reported significant increases in signal-to-noise (S/N) and/or spectral intensity compared to single-pulse (SP) LIBS. In addition to DP-LIBS, atmospheric conditions can also increase sensitivity. Thus, in this study, a collinear DP-LIBS scheme was used along with manipulation of the atmospheric conditions. The DP-LIBS scheme consisted of an initial 45 mJ pulse at 1064 nm fired into a sample contained in a controlled atmospheric/vacuum chamber. A second analytical 45 mJ pulse at 1064 nm was then fired 0 to 200 μs after and along the same path of the first pulse. Ar, He, and air at pressures ranging from atmospheric pressure to 1 Torr are introduced during DP-LIBS and SP-LIBS experiments. For a brass sample, significant increases in the spectral intensities of Cu and Zn lines were observed in DP-LIBS under Ar compared to DP-LIBS in air. It was also found that Cu and Zn lines acquired with SP-LIBS in Ar are nearly as intense as DP-LIBS in air. While collinear DP-LIBS is effective for increasing the sensitivity for some reduced atmospheres (i.e., Ar and air at 630 to 100 Torr and He at 300 Torr), the enhanced spectral intensity ultimately dropped off as the pressure was reduced below 10 Torr for all atmospheric compositions in the experimental arrangement used in this study. At all pressures of air and Ar, the plasma temperature remained rather constant with increased inter-pulse delays; however, the plasma temperature was more variable for different He gas pressures and inter-pulse delays.