Biorefining agro-industrial biomass residues for bioenergy production represents an opportunity for both sustainable energy supply and greenhouse gas (GHG) emissions mitigation. Yet, is bioenergy the most sustainable use for these residues? To assess the importance of the alternative use of these residues, a consequential life-cycle assessment (LCA) of 32 energy-focused biorefinery scenarios was performed based on eight selected agro-industrial residues and four conversion pathways (two involving bioethanol and two biogas). To specifically address indirect land-use changes (iLUC) induced by the competing feed/food sector, a deterministic iLUC model, addressing global impacts, was developed. A dedicated biochemical model was developed to establish detailed mass, energy, and substance balances for each biomass conversion pathway, as input to the LCA. The results demonstrated that even for residual biomass, environmental savings from fossil fuel displacement can be completely out-balanced by iLUC, depending on the feed value of the biomass residues. This was the case of industrial residues brewer's grain, beet residues, potato pulp, and whey. Overall, the GHGs from iLUC impacts were quantified to 4.1 t CO2-eq.ha-1demanded y-1 corresponding to 1.2-1.5 t CO2 t-1 dry biomass used for energy. Only bioenergy from straw and wild grass was shown to perform better than the alternative use, as no competition with the feed sector was involved. Biogas for heat-and-power production was the best performing pathway, in a short-term context. Focusing on transport fuels, bioethanol was generally preferable to biomethane considering conventional biogas upgrading technologies. Based on the results, agro-industrial residues cannot be considered burden-free simply because they are a residual biomass and careful accounting of alternative utilization is a pre-requisite to assess the sustainability of a given use. In this endeavor, the iLUC factors and biochemical model proposed herein can be used as templates and directly applied to any bioenergy consequential study involving demand for arable land.