One of the central challenges within education for sustainable development (ESD) is in empowering learners to reframe mindsets, particularly those that result in unsustainable behaviours and/or actions. This paper introduces the concept of rhizome articulated by Deleuze and Guattari (1987) and proposes that it can act as a framework for re-conceptualising processes of ESD. Key constructs within the rhizome, such as assemblages, nomadism, war machines and lines of flights, are discussed to highlight their relevance to ESD. The principles of the rhizome (connection, heterogeneity, multiplicity, signifying rupture, cartography and decalcomania) are then examined in the context of six processes necessary for effective ESD outlined by Tilbury (2011), namely, collaboration, dialogue, ‘whole system’ engagement, innovation within curricula, teaching and learning and active and participatory learning. The final section critically considers how this weaving of rhizomatic principles with the processes of ESD impacts on educating for sustainability. The rhizome has the potential to inspire educators and learners alike to become more critically aware of the interconnectivity and disruptive influences within sustainability. In this regard, the discussion ends by concluding that the reconceptualisation of ESD as rhizome or rhizomatic can foster an ontological shift towards perceiving the nature of reality as complex interconnected multiplicities.