The reconstruction of ancient atmospheric carbon dioxide concentrations is essential to understanding the history of the Earth and life. It is also an important guide to identifying the sensitivity of the Earth system to this greenhouse gas and, therefore, constraining its future impact on climate. However, determining the concentration of CO[subscript 2] in ancient atmospheres is a challenging endeavour requiring the application of state-of-the-art analytical chemistry to geological materials, underpinned by an understanding of photosynthesis and biochemistry. It is truly an interdisciplinary challenge. (Contains 5 figures and 1 box.)