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The pyrolysis (Py)-GC-MS technique was first introduced for the identification of two kinds of Chinese geographical indication vinegars because its advantages are that it is a simple and convenient sample pretreatment and inlet method. Abundant Py information about vinegars was obtained using Py-GC-MS; 21 common peaks were selected. With the help of the classical partial least-squares (PLS) modeling method for data analysis, two identification models for Shanxi extra-aged (SX) and Zhenjiang (ZJ) vinegars were established, respectively. An N-reducing method was used to select the variables. The variables were reduced one at a time to build the PLS models with the lowest number of misjudgments. Both models had good recognition rates, identifying over 90% of samples correctly. Thus, combining Py-GC-MS and PLS could be regarded as an effective method for the identification of SX and ZJ vinegars.