An increasing number of countries have introduced or plan to introduce policies to increase the proportion of biofuels within their energy portfolio. One impact is that biofuel production has been abruptly increasing for more than 5 years, leading to increasing number of production sites world-wide and also to diversification of processes and approaches to produce biofuel. There is today a large range of technologies currently available for producing so-called first-generation of biofuels and reasonably advanced processes that are dramatically expected for the production of biofuels that would use biomass that does not enter in competition with food and feed use. However, only very limited consideration has so far been given to safety issues. Nevertheless, risks exist throughout the biofuel life cycle. Although these safety issues do not actually represent a potential barrier on biofuel development, they deserve serious consideration. In this paper, we propose to rank the risks pertaining to biofuel chains by implementing a decision-making tool, BIOSAFUEL (R). From easily accessible input data, BIOSAFUEL (R) allows the user to build up a pre-diagnosis of the risks implicit to the whole life cycle of a given biofuel chain. We applied BIOSAFUEL (R) to first-generation bioethanol chains as a first case study. (C) 2008 Elsevier Ltd. All rights reserved.