Understanding the linkage between behaviour of mammals in their natural environment and the molecular basis of their sensory modalities presents challenges to biologists. Our olfactory investigations that involve the largest extant land mammal, the elephant, offer some clues of how these events mesh in sequence. Proboscideans have developed a sophisticatedly organized society and they rank with primates and cetaceans with respect to cognitive abilities. Our studies of discrete, quantifiable pheromone-elicited behaviours demonstrate that Asian elephants utilize their olfactory senses during fundamental, life-strategy decisions, including mate choice, female bonding and male hierarchical sorting. How biologically relevant odorants traverse mucous interfaces to interact with cognate odorant receptors remains a basic question in vertebrate olfaction. We have partially tracked the molecular odour reception trail of behaviourally distinct pheromones, (Z)-7-dodecenyl acetate and frontalin (1,5-dimethyl-6,8-dioxabicyclo[3.2.1]octane), using approaches developed for insect studies and taking advantage of the extensive, highly mucoidal olfactory and vomeronasal systems that permit detailed investigations of pheromone-binding proteins. We have combined studies of quantifiable responses and behaviours with biochemical and biophysical investigations of the properties of protein–ligand complexes, their sequential pathways and associated protein–ligand fluxes. In the delineation of these sequential integrations of behavioural, biochemical and molecular events, we have discovered novel spatial and temporal adaptations in both the main olfactory and vomeronasal systems.