The organic volatile components in fresh hawthorn were studied using simultaneous distillation extraction and gas chromatography-mass spectrometry (SDE-GC-MS). A total of sixty-one volatile components were identified, including 16 hydrocarbons, 16 alcohols, 10 aldehydes, 9 esters, 4 phenols, 3 ethers, 2 ketones, and 1 acid. These components were determined by MS and conformed by comparison of the retention times of the separated constituents with those of authentic samples and by comparison of retention indexes of separated constituents with the RIs reported in the literature. The predominant volatile component (over 2%) in fresh hawthorn was cis-3-hexenyl acetate (16.08%), followed by furfural (10.97%), α-terpineol (7.02%), 1,4-butanediol (5.92%), hexyl acetate (3.55%), eugenol (3.55%), and 1-methyl-4-(1-methylethenyl)-benzene (2.53%). From the odor characteristics of identified components, it can be known that the ester compounds, alcohol compounds, and aldehyde compounds were the characteristic volatile components of fresh hawthorn.