Bighead carp head soup is a traditional Chinese cuisine with a pleasant aroma, but the effect of fish head phospholipids (FPLs) on the odorants is not fully understood. In this study, nuclear magnetic resonance (NMR), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and headspace solid-phase microextraction gas chromatography–mass spectrometry (HS-SPME–GC–MS) were used to monitor the oxidation products of phospholipids in fish head soup during the cooking process, and the fish head triglycerides (FTGs) were used as controls. In 1H NMR spectra, the signals of unsaturated acyl groups and the oxidation compounds in FPLs were significantly higher than those in FTGs. The results of FTIR showed that the changes of functional group absorptions of the oxidation compounds in FPLs were greater than FTGs. GC–MS demonstrated that FPLs samples produced more lipid-derived volatile compounds than FTGs samples. These results showed that FPLs were more prone to oxidation and could produce more lipid-derived odorants. Therefore, FPLs rather than FTGs, were the main precursor substance of lipid-derived odorants in bighead carp head soup.