Headspace solid-phase microextraction (SPME) with an 85 µm Carboxen polydimethylsiloxane (CAR/PDMS) fiber was used to extract volatile compounds, and a gas chromatograph equipped with a mass spectometry detector (GC-MS) was used to identify the volatile compounds in honeys. Thirty-four different volatile compounds from the headspace of honey produced in the central valley of Ñuble Province, Chile, were extracted with fiber coating CAR/PDMS. The identified compounds were: 10 alcohols, 9 acids, 6 ketones, 3 aldehydes, 2 furans, 2 terpenes and 2 lactones. Only four of the volatile compounds had never been reported before as honey compounds; these being: 1,3-propanodiol, 2-methyl butanoic acid, 3,4-dimethyl-3-hexen-2-one, and 6-methyl-5-octen-2-one. These four compounds were found in three of the 10 analyzed samples. The compounds found in the highest percentage of area were ethanol, acetic acid, 1-hydroxy-2-propane, 3-hydroxy-2-butane, and furfural. However, the analyzed samples did not present a distinctive profile.