This study attempts to explore the suitable conditions for the detection of volatile flavor compounds (VFCs) in Ningxiang pork by headspace solid-phase microextraction and gas chromatography-mass spectrometry (HS-SPME-GC-MS). Ningxiang pigs were harvested from a slaughterhouse and a longissimus dorsi sample was collected from each animal. The VFCs of Ningxiang pork can be strongly impacted by the detection conditions (columns, weight of meat samples, heat treatment time, equilibrium conditions, and extraction conditions) that need to be optimized. Our results also provided the optimal test conditions: weighing 5 g of meat samples, grinding for 30 s in a homogenizer, heat treatment at 100 °C for 30 min, equilibration at 70 °C for 30 min, and extraction at 100 °C for 50 min. Furthermore, the feasibility and representativeness of the test method were confirmed based on principal component analysis and a comparison of the three pork VFCs. These findings offer researchers a unified and efficient pretreatment strategy to research pork VFCs.