The performance of spark ignition engines is highly dependent on fuel anti-knock quality, which in turn is governed by autoignition chemistry. In this study, we explore this chemistry for various aromatic oxygenates (i.e., anisole, 4-methyl anisole, 4-propyl anisole, guaiacol, 4-methyl guaiacol, 4-ethyl guaiacol) that can be produced from lignin, a low value residual biomass stream that is generated in paper pulping and cellulosic ethanol plants. All compounds share the same benzene ring, but have distinct oxygen functionalities and degrees of alkylation. The objective of this study is to ascertain what the impact is of said side groups on anti-knock quality and, by proxy, on fuel economy in a modern Volvo T5 spark ignition engine. To better comprehend the variation in behavior amongst the fuels, further experiments have been conducted in a constant volume autoignition device. The results demonstrate that alkylation has a negligible impact on anti-knock quality, while the addition of functional oxygen groups manifests as a deterioration in anti-knock quality.