Abstract Ignition delay times of four different primary reference fuels (PRF), mixtures of n-heptane and iso-octane, were measured behind reflected shock waves in a high-pressure shock tube facility. The PRFs were formulated to match the RON of two high-octane gasolines (RON 95 and 91) and two prospective low-octane naphtha fuels (RON 80 and 70). Experiments were carried out over a wide range of temperatures (700–1200 K), pressures (10, 20, and 40 bar) and equivalence ratios (0.5 and 1). Kinetic modeling predictions from four chemical kinetic mechanisms are compared with the experimental data. Ignition delay correlations are developed to reproduce the measured ignition delay times. Brute force sensitivity analyses are carried out to identify reactions that affect ignition delay times at specific temperature, pressure and equivalence ratio. The large experimental data set provided in the current work will serve as a benchmark for the validation of chemical kinetic mechanisms of primary reference fuel blends.