2-Hydroxymethylphenol (2-HMP) and 4-hydroxymethylphenol (4-HMP) were used as model compounds to study the reactions that occur during cure of phenol-formaldehyde (PF) resin to which cure accelerators (ethyl formate, propylene carbonate, gamma-butyrolactone, and triacetin) have been added. The addition of cure accelerators significantly increased the rate of condensation reactions. The cure accelerators were consumed during the reaction, indicating that they do not act as true catalysts. Major dimeric and trimeric reaction products were isolated and their structures determined. The results are consistent with a mechanism in which the hydroxyrnethyl group of 2-HMP (or 4-HMP) is first transesterified by the cure accelerator. The ester group is then displaced by reaction with the negatively charged ortho or para position of a second molecule (S,2 mechanism) or is converted to a reactive quinone methide intermediate, which subsequently reacts with the negatively charged ortho or para position of a second molecule (quinone methide mechanism). When accelerators were added to the reaction mixture, the self-condensation of 2-HMP was faster than that of 4-HMP. As is well documented in the literature, the exact opposite is true without added accelerators. This result would seem to indicate that the phenolic oxygen helps activate the esterified ortho-hydroxymethyl group. The number and nature of crosslinks in a PF resin cured with added cure accelerator might be different than those in a PF resin cured without an added cure accelerator.