Assessment of both economical and environmental performance of biofuel supply chains is crucial to have a complete view of the future implications of those systems. This paper presents a multi-objective, static modelling framework for the optimisation of hybrid first/second generation biofuel supply chains. Using the proposed modelling framework, different aspects are analysed including the potential GHG savings, the impact of carbon tax on the economic and environmental performance of a biofuel supply chain, the trade-off between the economic and environmental objectives and the maximum bioethanol throughput that can be achieved at different cap levels on the total supply chain cost. The trade-off between the conflicting objectives is analysed by solving the proposed multi-objective model using the epsilon-constraint method. In addition, the impact of technological learning on the economic and environmental performance of the supply chain throughout time is also analysed using a multi-period model developed based on the proposed static optimisation framework. Bioethanol production in the UK using hybrid first/second generation technologies is considered as the case study to highlight the model applicability. (c) 2012 Elsevier Ltd. All rights reserved.