The volatile compounds of 10 Piper species cultivated in Hainan Island, China, have been investigated. Eighty compounds were profiled after headspace-solid phase microextraction (HS-SPME) with gas chromatographymass spectrometry (GC-MS). Mean Bray-Curtis similarity value was only 22.78 ± 1.98% among the different Piper species. The volatile compounds were largely grouped as hydrocarbons, aldehydes, alcohols, acids, ketones, esters, and phenols. The main compounds comprised benzaldehyde, cinnamaldehyde, β-caryophyllene, ocimene, lavandulol, myrcene, cubebene, terpinene, linalool, α-caryophyllene, β-elemene, and germacrene. Principal component analysis revealed that Piper laetispicum, Piper longum, Piper hainanense, Piper betle, and Piper flaviflorum were characterized by high contents of β-caryophyllene, α-caryophyllene, germacrene, and β-pinene. Piper puberulum and Piper cathayanum were associated with high contents of linalool, myrcene, and germacrene D. On the other hand, Piper pseudofuligineum and Piper retrofractum were related with high contents of ocimene. Finally, Piper auritum was associated with high content of cinnamaldehyde. Volatile profiling of Piper species by HS-SPME-GC-MS and the interrelationship investigated among the volatiles can be used as a roadmap for future resource utilization or biotechnological applications.