Bacteria and endogenous enzymes generate volatile organic compounds (VOCs), which are posited to be the primary source of undesirable flavors in spoilt pork. Headspace solid-phase microextraction–gas chromatography–mass spectrometry (HS-SPME-GC-MS) was employed to assess the fluctuations in VOC concentrations in pork stored under tray packaging at 6–8 °C for 10 days, while total volatile basic nitrogen (TVB-N) and total viable counts (TVCs) were used to determine the quality of the pork. During storage, TVCs steadily increased, reflecting the growth of spoilage-related microorganisms, while TVB-N levels surpassed the spoilage threshold early, indicating an acceleration of the degradation process. Nine VOCs associated with pork spoilage were found by partial least squares discriminant analysis (PLS-DA), fold change (FC), and t-tests. The substances comprised ethyl acetate, acetoin, 3-methyl-1-butanol, 3-methylbutanal, 1-octen-3-ol, hexanal, vinyl acetate, 2-methylaziridine, and heptanal. A univariate linear regression analysis revealed a strong positive correlation (p < 0.001) between the gaseous total volatile basic nitrogen (G-TVBN) and the storage duration. Given that G-TVBN accurately reflects changes in pork freshness and the progression of spoilage, these results highlight the potential for dynamically monitoring the freshness and spoilage processes of pork.