A numerical and experimental investigation in to the role of gasoline surrogates and their reduced chemical kinetic mechanisms in spark ignition (SI) engine knocking has been carried out. In order to predict autoignition of gasoline in a spark ignition engine three reduced chemical kinetic mechanisms have been coupled with quasi-dimensional thermodynamic modelling approach. The modelling was supported by measurements of the knocking tendencies of three fuels of very different compositions yet an equivalent Research Octane Number (RON) of 90 (ULG90, PRF90 and 71.5% by volume toluene blended with n-heptane) as well as iso-octane. The experimental knock onsets provided a benchmark for the chemical kinetic predictions of autoignition and also highlighted the limitations of characterisation of the knock resistance of a gasoline in terms of the Research and Motoring octane numbers and the role of these parameters in surrogate formulation. Two approaches used to optimise the surrogate composition have been discussed and possible surrogates for ULG90 have been formulated and numerically studied. A discussion has also been made on the various surrogates from the literature which have been tested in shock tube and rapid compression machines for their autoignition times and are a source of chemical kinetic mechanism validation. The differences in the knock onsets of the tested fuels have been explained by modelling their reactivity using semi-detailed chemical kinetics. Through this work, the weaknesses and challenges of autoignition modelling in SI engines through gasoline surrogate chemical kinetics have been highlighted. Adequacy of a surrogate in simulating the autoignition behaviour of gasoline has also been investigated as it is more important for the surrogate to have the same reactivity as the gasoline at all engine relevant p−T conditions than having the same RON and Motored Octane Number (MON).