Papilionid butterflies of the tribe Troidini are specialists on plants of the family Aristolochiaceae. The role of plant volatiles in host recognition by adult and larval stages of these insects remains unknown. We used Battus polydamas archidamas (Papilionidae: Troidini) and its host-plant, Aristolochia chilensis (Aristolochiaceae), to study: (i) the olfactory and electrophysiological responses of adults to headspace volatiles of the host-plant, (ii) the chemical composition of the headspace volatiles of the host-plant, (iii) the patterns of aggregation of larvae in the field in order to ascertain the time when they leave the plant where the eggs were laid, and (iv) the olfactory responses of solitary-feeding fourth-instar larvae to headspace volatiles of the host-plant. Larvae left their initial host-plant during the third or fourth instar. Host-plant headspace volatiles attracted fourth-instar larvae as well as adults; adult females were more responsive than males. Taken together, these results reveal changes in the responsiveness to host-plant volatiles during development, and provide an insight into the host-plant specialization of this butterfly.