Aroma is an important quality indicator for apples and has a great influence on the overall flavour and consumer acceptance. However, the information of the aroma volatile compounds in apple peels is largely unknown. In this study, evaluation of volatile compounds in peels of 40 apple cultivars was carried out using headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS). A total of 78 volatile compounds were identified, including 47 esters, 12 aldehydes, 5 alcohols, 3 ketones, 1 acid and 10 others. Eight volatile compounds were common in all apple cultivars. Cultivar Changfu No. 2 contained the highest number of volatile compounds (47), while Qinyue contained the least (20). Honey Crisps had the highest volatile content, at 27,813.56 ± 2310.07 μg/kg FW, while Huashuo had the lowest volatile content, at 2041.27 ± 120.36 μg/kg FW. Principal component analysis (PCA) clustered the 40 apple cultivars into five groups. Aroma is cultivar-specific, volatile compounds of hexyl butyrate, hexyl 2-methylbutyrate and hexyl hexanoate, together with hexanal, (E)-2-hexenal, 1-hexanol, estragole and α-farnesene could be proposed for apple cultivar classification in the future.