In this paper, new experimentally determined octane numbers (RON & MON) of blends of a 3-component surrogate consisting of Toluene, n-Heptane, i-Octane (called toluene reference fuel—TRF) arranged in an augmented simplex design are used to derive a simple response surface model for the octane number of any arbitrary TRF mixture. The model is second-order in its complexity and is shown to be more accurate to the standard "Linear by Volume" (LbV) model which is often used when no other information is available. This is due to the existence of both synergistic and antagonistic blending of the octane numbers between the three components. In particular, antagonistic blending of toluene and iso-octane leads to a maximum in sensitivity that lies on the toluene/iso-octane line. The model equations are inverted so as to map from RON/MON space back into composition space. This allows one to use two simple formulae to determine, for a given fuel with known RON and MON, the volume fractions of toluene, n-heptane and iso-octane to be blended in order to emulate that fuel. HCCI engine simulations using gasoline with a RON of 98.5 and a MON of 88 were simulated using a TRF fuel, blended according to the derived equations to match the RON and MON. The simulations matched the experimentally obtained pressure profiles well, especially when compared to simulations using only PRF fuels which matched the RON or MON. This suggested that the mapping is accurate and that to emulate a refinery gasoline, it is necessary to match not only the RON but also the MON of the fuel.