In the present study, flavor profiles of Chinese spiced beef in the cooking process were comparatively analyzed by electronic nose, gas chromatography–mass spectrometry (GC–MS) with a thermal desorption system (TDS), and solid-phase microextraction (SPME). A total of 82 volatile compounds were identified, and 3-methyl-butanal, pentanal, hexanal, ρ-xylene, heptanal, limonene, terpinene, octanal, linalool, 4-terpinenol, α-terpineol, and (E)-anethole were identified as the characteristic flavor compounds in Chinese spiced beef. Variation in the content of volatile components produced by different cooking processes was observed. In general, a cooking time of 4 h resulted in optimal flavor quality and stability. Results indicated that the electronic nose could profile and rapidly distinguish variation among different cooking time. The volatile profiling by TDS-GC–MS and responses from the electronic nose, in combination with multivariate statistical analysis, are a promising tool for control the cooking process of spiced beef.