Abstract: Compound-specific isotope analysis (CSIA) of individual organic compounds is a powerful but underutilized tool in petroleum exploration. When integrated with other organic geochemical methodologies it can provide evidence of fluid histories including source, maturity, charge history and reservoir processes that can support field development planning and exploration efforts. The purpose of this chapter is to provide a review of the methodologies used for generating carbon and hydrogen isotope data for mid- and high-molecular-weight n -alkanes. We discuss the factors that control stable carbon and hydrogen isotope compositions of n -alkanes and related compounds in sedimentary and petroleum systems and review current and future applications of this methodology for petroleum exploration. We discuss basin-specific case studies that demonstrate the usefulness of CSIA either when addressing particular aspects of petroleum exploration (e.g. charge evaluation, source rock–oil correlation, and investigation of maturity and in-reservoir processes) or when this technique is used to corroborate interpretations from integrated petroleum systems analysis, providing unique insights which may not be revealed when using other methods. CSIA of n -alkanes and related n -alkyl structures can provide independent data to strengthen petroleum systems concepts from generation and expulsion of fluids from source rock, to charge history, connectivity, and in-reservoir processes.