Due to its compatibility with the current energy infrastructures and the potential to reduce CO2 emissions significantly, CO2 capture and geological storage is recognised as one of the main options in the portfolio of greenhouse gas mitigation technologies being developed worldwide. The CO2 capture technologies offer a number of alternatives, which involve different energy consumption rates and subsequent environmental impacts. While the main objective of this technology is to minimise the atmospheric greenhouse gas emissions, it is also important to ensure that CO2 capture and storage does not aggravate other environmental concerns. This requires a holistic and system-wide environmental assessment rather than focusing on the greenhouse gases only. Life Cycle Assessment meets this criteria as it not only tracks energy and non-energy-related greenhouse gas releases but also tracks various other environmental releases, such as solid wastes, toxic substances and common air pollutants, as well as the consumption of other resources, such as water, minerals and land use. This paper presents the principles of the CO2 capture and storage LCA model developed at Imperial College and uses the pulverised coal post-combustion capture example to demonstrate the methodology in detail. At first, the LCA models developed for the coal combustion system and the chemical absorption CO2 capture system are presented together with examples of relevant model applications. Next, the two models are applied to a plant with post-combustion CO2 capture, in order to compare the life cycle environmental performance of systems with and without CO2 capture. The LCA results for the alternative post-combustion CO2 capture methods (including MEA, K+/PZ, and KS-1) have shown that, compared to plants without capture, the alternative CO2 capture methods can achieve approximately 80% reduction in global warming potential without a significant increase in other life cycle impact categories. The results have also shown that, of all the solvent options modelled, KS-1 performed the best in most impact categories.