Bamboo vinegar is a liquid biomass with a huge yield and complex chemical composition. At present, the relative quantification of bamboo vinegar has been investigated in most studies. To analyze twelve compounds from bamboo vinegar simultaneously, gas chromatography-mass spectrometry and an external standard method were used to develop an analytical method. In this method, chromatographic separations of all compounds were above 1.5. The linear range was between 0.100 and 10.000 mg/L, and the coefficient of determination (R2) was between 0.9981 and 0.9997, indicating a good linear relationship. The limit of detection (LOD) was between 0.004 and 0.780 mg/L; the limit of quantitation (LOQ) was between 0.016 and 3.120 mg/L; the relative standard deviations (RSDs) of instrument precision and method stability were less than 8%; the recovery rate was between 89.25% and 113.77%, and its RSD was between 0.44% and 5.70%. Using this method, fourteen bamboo vinegars and six wood vinegars were analyzed, and it was found that the content of propionic acid, phenol, and 2-methoxyphenol was higher in most samples. In addition, the differences in physicochemical properties between distilled bamboo vinegar and its original solution after atmospheric distillation were investigated.