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The bio-economy is characterised by aspirations of replacing the fossil-based economy with biobased energy, resources and processes; biofuels are particularly popular. This new shift comes with multiple risks and uncertainties in both industrialised and developing economies. The uptake of biofuels is inextricably linked to and legitimised by policy processes involving a complicated nexus of vested interests, political aspirations, and technological drivers, and a range of associated factors. In this paper we describe the characteristics of and contours along which two national biofuels policies in India and South Africa have been articulated and developed. In doing so we establish how a biofuels regime has gained legitimacy, becoming embedded into policy processes dictated largely through specific networks and reflective of the rationalising effect of global and local narratives. We analyse how pro-poor 'win-win' narratives gained purchase amongst different actors and in turn how they were used as a basis for biofuels policies. The case studies are, however, complex and differentiated, pointing towards sociopolitical nuances and structural subtleties. [ABSTRACT FROM AUTHOR]