Flavor is critical to the commercial acceptance of the highly valued Chinese mitten crab (Eriocheir sinensis). This study investigated the important odorants (IOs) in male E. sinensis hepatopancreas formed from phosphatidylethanolamine (PE) in model systems. A total of fifteen IOs were detected by gas chromatography-mass spectrometry-olfactometry (GC-MS-O). Among the IOs that were also detected as oxidation products of PE extract were hexanal, heptanal, nonanal, 2-pentylfuran and 2-octanone, and the optimized oxidation conditions of PE extract were 175 °C for 60 min. For further analysis, nine PE species were considered important precursors of IOs in E. sinensis. Odorants derived from PE (16:0/18:2), PE (18:0/18:2), PE (18:0/20:4), PE (16:0/22:6), and PE (18:0p/22:6) specie standards were detected, and their oxidative stabilities are discussed. These findings are important for understanding the comprehensive formation mechanism of IOs in E. sinensis, which may provide theoretical guidance for improving the overall flavor of aquatic products.