Human head lice Pediculus humanus capitis (De Geer) (Phthiraptera: Pediculidae) are insect parasites closely associated with humans, feeding on the blood of their hosts and causing them skin irritation and probable secondary infections. Despite being a severe nuisance, very few studies have reported on intraspecific chemical communication in head lice. Here, we evaluated the attractive response of head lice to the volatile compounds and solvent extracts from their feces. We also chemically analyzed the main volatile components of these feces and those of the feces' extracts. Head lice were attracted to the methanol extract of their feces but not to the hexane or dichloromethane extracts, suggesting the polar nature of bioactive chemicals present in head louse feces. Follow-up chemical identifications, in fact, showed the presence of hypoxanthine, uric acid, and another purine tentatively identified as either guanine or iso-guanine. Additionally, head lice were significantly attracted by volatiles emitted from samples containing feces. The volatiles emanated from feces alone contained 19 identified substances: 2-pentanone, hexanal, heptanal, 3-methyl-3-buten-1-ol, octanal, sulcatone, nonanal, acetic acid, 2-ethyl-1-hexanol, decanal, 1-octanol, butyric acid, 1-nonanol, hexanoic acid, octanoic acid, 2,6-dimethyl-7-octen-2-ol, 2-undecanone, geranylacetone, and hexadecane. The major compounds found were decanal, nonanal, hexanal, and acetic acid, together representing approximately 60% of the identified compounds. This work represents the first chemical evidence of intraspecies communication among head lice. The results support the existence of active substances present in the feces of P. humanus capitis that may be involved in its aggregation behavior.