Aroma in food plays an important role in food perception and acceptance, which depends on various mixtures of volatile organic compounds (VOCs). Moreover, VOCs are of great significance for aroma identification. In this study, headspace solid-phase microextraction (HS-SPME) combined with gas chromatography–mass spectrometry (GC-MS) technology was used to determine the VOCs in 10 pear syrups. A total of 127 VOCs were quantitatively determined, including 9 common VOCs and 46 characteristic VOCs of 10 pear syrups. The pear syrups were divided into three categories by cluster analysis, and thirty-eight differential VOCs were obtained using orthogonal partial least squares discrimination analysis (OPLS-DA) and fourteen key VOCs were selected by odor activity value (OAV). It was revealed that the key and common aroma components of pear syrups were butanoic acid, methyl ester, 2-methyl-, methyl ester and Hexanoic acid, and ethyl ester. The characteristic and differential VOCs were 10-Undecen-1-ol, Hexadecanal, n-Propylacetate, Cyclohexanol, 5-methyl-2-(1-methylethyl)-, (1S,2R,5S)-, Methional, Disulfide, dimethyl, 8-Nonenoic acid, ethyl ester, Naphthalene, 1,2-dihydro-1,1,6-trimethyl-, 3H-Purin-6-amine, N,N,3-trimethyl-, 2-Octanol,2,6-dimethyl-, Furyl hydroxymethyl ketone, Heptane, 2,2,4,6,6-pentamethyl-, and Butanoic acid,2-methyl-,methyl ester. The above results showed that different pear syrups had rich diversity in aroma compounds, with some components being shared among them while others are exclusive to specific syrups.