Based on hydrophilic interaction liquid chromatography (HILIC) liquid chromatography−mass spectrometry (LC− MS), untargeted differential metabolomics analysis was performed on the pear wine samples before and after browning to determine the key compounds that affect the browning of Dangshan pear wine. A total of 196 significantly differential metabolites were found, 22 of which might be related to the browning of Dangshan pear wine. D-(+)-glucose, L-phenylalanine, L-norleucine, methionine, D-(+)-proline, aloin, and rutin were the key differential metabolites in pear wine before and after browning. The Maillard reaction of D-(+)-glucose, L-norleucine, methionine, and the oxidation of aloin played critical roles in the browning of Dangshan pear wine. The reaction of aloin and glucose to form 5-hydroxyaloin A, 7-hydroxyaloin B, and elgonica-dimer A was one of the important metabolic pathways in which the phenolic compounds formed anthraquinone during the browning process of Dangshan pear wine.