Volatile constituents of ripe fruits of 16 Capsicum accessions from the annuum-chinense-frutescens complex, with different aroma impressions and geographical origins, were isolated by headspace-solid phase microextraction (HS-SPME) and analyzed by gas chromatography-olfactometry-mass spectrometry (GC-sniffing port-MS). More than 300 individual compounds could be detected in the studied genotypes; most of them could be identified by comparing mass spectra and retention times with authentic reference substances or literature data. Esters and terpenoids were the main groups, although other minor compounds, such as nitrogen and sulfur compounds, phenol derivatives, norcarotenoids, lipoxygenase derivatives, carbonyls, alcohols, and other hydrocarbons, were also identified. The sniffing test revealed that the diversity of aromas found among the studied cultivars is due to qualitative and quantitative differences of, at least, 23 odor-contributing volatiles (OCVs). C. chinense, and C. frutescens accessions, with fruity/exotic aromas, were characterized by a high contribution of several esters and ionones and a low or nil contribution of green/vegetable OCVs. Different combinations of fruity/exotic and green/vegetable OCVs would explain the range of aroma impressions found among C. annuum accessions. Implications of these findings for breeding and phylogeny studies in Capsicum are also discussed.