Second-generation (2G) biofuels are promoted worldwide as remedy to sustainable-energy challenges in the transport sector and as response to the criticism of first-generation biofuels. By utilizing agriculture and forest residues, 2G biofuels claim to support agricultural livelihoods and boost rural economies. Quantitative estimates exist of the availability of “waste” or “unused” or “surplus” biomass that could be fed into producing bioenergy. Most of current discourse on 2G bioethanol is about developing efficient technologies and supportive policies for biomass utilization and energy distribution, while availability and supply of that biomass are often taken for granted. This paper challenges these presumptions of biomass availability and technological feasibility.