Permeation of water vapor, oxygen, nitrogen, and carbon dioxide through polymer films is measured by the programed valving mass spectrometry (PVMS) method. The results are calibrated with a standard permeation rate for each gas to determine the detection sensitivity. The calibrated lower detection limits are 1.90×10?7?g/m2?day for water vapor, 2.81×10?2?cm3/m2?day for oxygen, 2.15×10?2?cm3/m2?day for nitrogen, and 3.29×10?2?cm3/m2?day for carbon dioxide. The lower detection limits presented here for water vapor, nitrogen, and carbon dioxide are more than two orders of magnitude lower than the corresponding values offered by the NIST-traceable standard techniques. In addition, the PVMS water vapor lower detection limit meets the sensitivity requirement for detecting “ultrabarrier” water vapor permeation rates, while the oxygen lower detection limit is higher than that offered by the standard technique. However, the results suggest a modified measurement protocol and/or system modifications to overcome this limitation. Effusivity through a flow orifice was also examined using the PVMS method for the above gases. The effusion results from the flow orifice, combined with the permeation results from polymer samples, provide insight into the factors that may influence gas detection sensitivities.