Systems and methods for determining olefin concentrations in olefin-containing fuels (e.g., gasoline) are described. Generally, a Raman spectrum from a linear-calibration reference sample (e.g., a pure hydrocarbon, such as toluene) and Raman spectra from multiple simulated fuel samples having known olefin concentrations are obtained. An area ratio for each simulated fuel sample is created by dividing the area in the olefin region of each fuel sample by the area in the chemical spectral region of the linear-calibration reference sample. The area ratio and the known olefin concentration for each simulated sample are used to create a linear olefin calibration. The olefin concentration of a fuel sample with an unknown olefin concentration is calculated by determining the area ratio between the olefin spectral region in the unknown sample and the chemical spectral region in a concentration-calculation reference sample (e.g., toluene) and placing the new area ratio into the linear olefin calibration.