Abstract: This paper provides an overview of the role that geochemistry plays in petroleum systems analysis, and how this can be used to derive constraints on the key elements and processes that give rise to a successful petroleum system. We discuss the history of petroleum geochemistry before reflecting on the next frontier in geochemical applications in hydrocarbon systems. We then review the individual contributions to this Special Publication. These papers present new geochemical techniques that allow us to develop a more systematic understanding of critical petroleum system elements; including the temperature and timing of source-rock deposition and maturation, the mechanisms and timescales associated with hydrocarbon migration, trapping, storage and alteration, and the impact of fluid flow on reservoir properties. Finally, we provide a practical example of how these different geochemical techniques can be integrated to constrain and generate a robust understanding of the prolific Paleozoic petroleum system of the Bighorn Basin.