The Banisteriopsis caapi vine (Malpighiaceae) and the Psychotria viridis shrub (Rubiaceae) are the principal botanical species historically appropriated in a ritual context by several indigenous groups and caboclos in the Amazon. The cultural phenomenon represented by the Brazilian Ayahuasca religions – Daime, Barquinha and União do Vegetal – has given rise to an intense diaspora of plants and knowledge. Different varieties of these botanical species were transferred from the Amazon and introduced in the most diverse ecological contexts throughout the country. Through qualitative methods associated with Ethnobotany, this study examines folk taxonomy and the circulation of knowledge around the sacred plants used in the context of Santo Daime. Environmental history of ayahuasca is revealed through travel literature of the colonial Amazon. The main ethnobotanical varieties of jagube and rainha are characterized. Taxonomic knowledge is examined around these botanical entities. Their phytogeographic expansion is contemplated. From the infernal brebaje to the religious sacrament, ayahuasca and the plants that compose it are established in history as polyphonic, polysemic and polycentric entities. A classification system based on sensitive and supersensitive criteria characterizes the caboclo taxonomy of the sacred Amazonian plants of Daime. Ethnobotanical knowledge suggests that plant morphology corresponds to the cognitive center of taxonomic processes in this tradition. Supersensitive attributes mobilized in the classification acts of these botanical entities are similarly perceived as legitimate taxonomic criteria. More than a dozen varieties of jagube and at least six distinct morphological types of rainha are appropriate to this cultural context. The expansion of vine and leaf plantations under the principles of synthropic agriculture and the improvement of the practices of feitio are the principal strategies aimed at the material sustainability of Daime. The cultivation of jagube and rainha mobilizes a matrix of formal scientific knowledge and complex traditional knowledge constituted in intimate contact with material and spiritual aspects of the forest. The ecological ethos of the Ayahuasca peoples manifests itself in connection with their knowledge of the forest, a sacred territory, where the spiritual nutrient of good living grows. Keywords: Sacred Plants. Ayahuasca. Botanical Knowledge. Sustainability. Santo Daime.