This article describes the catalytic effect of NaHCO3 on condensation reactions of monomeric hydroxymethylphenols (HMPs) to elucidate the cure-acceleration mechanism. By comparison of the kinetics of self-condensations of HMPs, NaHCO3 was proved to increase the reactivity of para-hydroxymethyl groups. The changes of 13C nuclear magnetic resonance (NMR) chemical shifts on each HMP system with the additive indicated that the addition of NaHCO3 enhanced some molecular interactions between HMPs and NaHCO3, facilitating a resonance effect that might play a similar role in dissociation of the phenolic hydroxyl groups of HMPs. In addition, computational modeling by molecular orbital calculations elucidated that hydrogen carbonate anion (Symbol) forms an interaction between either the para-hydroxymethyl group and the phenolic hydroxyl group or between the two para-hydroxymethyl groups of HMPs by hydrogen bonds. From the experimental results, the authors proposed the mechanism of the catalytic action of NaHCO3: it appears to be due to the delocalization of an electron initiated by the interaction of the para-hydroxymethyl groups and the phenolic hydroxyl of HMPs with Symbol through hydrogen bonds, which results in facilitating the formation of active species.