Abstract Petiveria alliacea L., Phytolaccaceae, a plant used in Afro-Brazilian religious smoke rituals is reported to have "harmonic properties" (anxiolytic effect) by ethnobotanical survey. In the present work, we analyzed the chemical composition of volatiles produced by leaves of P. alliacea, using headspace gas chromatography/mass spectrometry and its potential anxiolytic and toxic effects in smoke-exposed rats. Locomotor activity and anxiety-like behavior were allocated into groups, according to substance administration: acute (locomotor activity) or chronic (anxiety-like behavior) burning charcoal or to smoke from P. alliacea. Inflammatory cell counts in the bronchoalveolar lavage and morphometric analysis in airway were assessed. Animals exposed to P. alliacea smoke had no locomotor activity or elevated plus maze open arm exploration impairment, while lungs had lower number of macrophages in bronchoalveolar fluid and an increased number of mononuclear and polymorphonuclear cells in the peribronchovascular region. Chemical analysis of plant material allowed the identification of dimethylsulfide (18.7%), diethylsulfide (33.4%) and nerolidol (25.8%) as main volatile compounds. Taken together, prolonged exposure to P. alliacea smoke does not induce anxiolytic effects, but histological analyses indicate a possible pulmonary inflammatory response.