During thermal utilization of biomass, a complex array of reactions ensues in the oxidative environment between fragments of the biomass and reactive species. In the low-temperature window, hydroperoxyl (HO[Formula: see text] radicals assume a central role prior to the establishment of the O/H radical pool. Anisole, cresol, guaiacol and vanillin are often utilized as representative model compounds to comprehend the combustion chemistry of the phenolic entities in biomass and oxygen-containing derived bio-oil. This paper reports thermo-kinetic parameters for the reactions of HO2 radicals with anisole, cresol, guaiacol and vanillin. Computed activation enthalpies entail facile values for H abstraction from the side-chain functional groups in the investigated compounds. H abstraction from the hydroxyl groups incurs lower activation energies in reference to methyl sites in cresol and guaiacol. Hence, H abstraction from the OH sites in these two molecules proceeds at a faster reaction rate constant when compared to abstraction from the methyl site. In the vanillin molecule, abstraction from the aldehydic and hydroxyl sites portrays comparable importance. The effect of scaling vibrational frequencies and the type of applied quantum tunneling on the computed reaction rate constants were thoroughly explored. Analysis of entropies of activation indicates that the transition states exhibit a product-like character. While ignition delay times of fuels often exhibit a profound sensitivity towards initial H abstraction reactions by HO2, we found that ignition delay times of the four title molecules remain almost unchanged when updating literature kinetics models with new reaction rate constants calculated herein. It is anticipated that reported outcomes from this study aid in formulating a better understanding of the complex chemical reactions that dictate oxidative decomposition of oxygenated bio-oil model compounds.