The unique flavour contribution of higher alcohols in alcoholic beverages has received growing attention; however, there is a dearth of information on their in vivo metabolic kinetics. In this study, the composition and content of higher alcohols in different alcoholic beverages from Chinese Baijiu and Lujiu were studied via in vivo analysis using Bama pigs to elucidate the mechanisms for intoxication of alcohol in vitro and in drinkers. Direct injection combined with gas chromatography–mass spectrometry (GC-MS) were used to accurately quantify a total of 14 higher alcohols in five alcoholic beverages. Based on the external standard method, a total content of 289.37–938.33 mg/L was detected, mainly 1-butanol, 3-methyl-1-butanol, 1-hexanol, 2-methyl-1-propanol and 2-butanol. Then, headspace solid-phase microextraction (HS-SPME) and solid-phase extraction (SPE) combined with GC-MS analysis strategy, respectively, were adopted to continuously monitor the changes in the concentrations of ethanol and 11 higher alcohols in the blood within 24 h after gavage of different alcoholic beverages, and the key pharmacokinetic parameters were analysed. The peak concentration (Cmax) and area under curve (AUC) of blood higher alcohols were significantly lower than those of ethanol (p < 0.05), accompanied by a later peak time (Tmax) and a larger apparent clearance rate (CL_F), and there were certain differences between the same higher alcohols in different alcoholic beverages and between different higher alcohols in the same alcoholic beverage. This work provides valuable insights into the metabolism of alcoholic beverages.