To detect the flavor quality and flavor compounds in raw longissimus muscle from four typical pig breeds: Sus scrofa × Bamei pig named F1 (group A), F1 × F1 (group B), F1 × Bamei pig (group C), and F1 × Large White (group D). The chemical compositions of longissimus muscles from four breeds were examined using headspace solid-phase microextraction/gas chromatography mass spectrometry method. Distinct differences for the same flavor compounds of longissimus muscles between different breeds were analyzed. Totally 64 flavor compounds shared in four groups, and 10 flavor compounds with significant difference among four groups (p < 0.05), including allyl butyrate, (Z)-2-penten-1-ol, 2,2-dimethyl-3-methyl oxirane, 2-pentylfuran, dodecane, 2,4-decadienal, vinylsilane, 3-methyl-1-butanol, (1-methyldecyl)-benzene, and dipropyl phthalate. Totally, 23–41 flavor compounds did not commonly exist in four groups, such as only as dibutyl isophthalate in group A; 6,10-dimethyl-5-9-undecadien-2 one, bis (2-trimethylsilyl) ethyl ester-malonic acid, heptadecane, 2,4,6-trimethyl pyridine, and diisooctyl adipate in group C alone; and 1,3-dimethylcyclopentanol, 2-octanone, and trimethylsilane in group D alone. While, no specific flavor compounds were identified in group B. All these flavor compounds covered 12 types of hydrocarbons, alcohols, aldehydes, hydroxybenzenes, acids, ketones, esters, sulfides, furans, alkenes, and pyrrole. Besides, we analyzed 14 flavor compounds with different flavors combining with previous studies. The flavor compounds in longissimus muscles might be closely related to the breeds, and the hybrid of S. scrofa × Bamei pig had the most flavor compounds in raw longissimus muscle.