Abstract The present experimental investigation aims to understand the homogeneous combustion chemistry associated with binary blends of three surrogate components for practical fuels, including toluene, isooctane, and diisobutylene-1 (DIB-1). Specifically, high-pressure autoignition characteristics of the three neat fuel components as well as the fuel blends of toluene + isooctane and toluene + DIB-1 are studied herein. Experiments are conducted in a rapid compression machine at compressed pressures varying from 15 to 45 bar and under low to intermediate temperatures. To obtain insights into interactions among fuels, the relative proportion of the two neat fuels in the reactive mixtures is systematically varied, while the total fuel mole fraction and equivalence ratio are kept constant. Experimental results demonstrate that ignition delays for neat toluene are more than an order of magnitude longer than those for neat isooctane. Whereas DIB-1 has ignition delays shorter than those for isooctane at higher temperatures, at temperatures lower than 820 K DIB-1 shows a longer ignition delay. Although the ignition delays of binary blends lie in between the two extremes of neat components, the variation of ignition delay with the relative fuel proportion is seen to be highly nonlinear. Especially, a small addition of isooctane or DIB-1 to toluene can result in greatly enhanced reactivity. In addition, the effect of DIB-1 addition to toluene is more significant than the effect of isooctane addition. Furthermore, in the compressed temperature range from 820 to 880 K, ignition delay of the toluene + isooctane blend shows greater sensitivity to temperature than that of isooctane.