Abstract: Two mass spectrometry (MS) methods, solid-phase microextraction gas chromatography (SPME–GC–MS) and direct analysis in real time (DART-MS), have been explored to investigate widespread efflorescence observed on exhibited objects at the Smithsonian’s National Museum of the American Indian in New York (NMAI-NY). Both methods show great potential, in terms of speed of analysis and level of information, for identifying the organic component of the efflorescence as 2,2,6,6-tetramethyl-4-piperidinol (TMP-ol) emitted by the structural adhesive (Terostat MS 937) used for exhibit case construction. The utility of DART-MS was proven by detecting the presence of TMP-ol in construction materials in a fraction of the time and effort required for SPME–GC–MS analysis. In parallel, an unobtrusive SPME sampling strategy was used to detect volatile organic compounds (VOCs) accumulated in the exhibition cases. This sampling technique can be performed by collections and conservation staff at the museum and shipped to an off-site laboratory for analysis. This broadens the accessibility of MS techniques to museums without access to instrumentation or in-house analysis capabilities.