Providing food, energy and materials for the rising global population is a challenge which is compounded by increased pressure on natural resources such as land, water and fossil sources of raw materials. Greenhouse gas (GHG) emissions from human activities have increased with industrial development and population expansion, and it is anticipated that resulting climate change might further limit agricultural productivity, through changes to weather patterns and global availability/distribution of agriculturally productive land. Growing crops as feedstocks for industrial uses is seen as one way of reducing GHG emissions and dependency on fossil resources. However, determining the extent to which the development of crops for industrial use will effect GHG balances and provide for a more energy efficient manufacturing system requires the development and use of appropriate calculation methodologies. Research at the Porter Institute has identified over 250 different scenarios for bioenergy production systems using commodity crops. In order to rationalise this complexity and diversity, a modular approach to Life Cycle Assessment (LCA) and sustainability analysis has been taken. This allows characterisation of discrete sections of supply chains and enables comparisons to be made between different crop production systems, different process systems and different end product uses. The purposes of this paper are to introduce the concepts of biofuel GHG and sustainability metrics, to introduce the approach taken by our organization and to use the example of UK grown willow in a lignocellulosic ethanol production system to demonstrate how GHG emission outcomes can be reviewed for “new” crops and technologies. The results show a range of variation, in both growing and process systems and how outcomes such as energy and GHG balances can be affected by various activities. LCA methodologies provide data to inform governments and industry of the potential specific supply chains may have for energy and GHG saving. However, methodological approaches can also affect assessment outcomes. Unresolved issues in LCA methodology must also be evaluated e.g. impacts resulting from land use change. Sustainability assessments of crop growing systems, irrespective of the end use, also assist in the assessment of environmental impacts of supply chains. However, it is critical that data continue to be collected, analysed and reviewed, to ensure that the most appropriate crops are grown and processed for the most appropriate end use.