Resol type phenolic resin/layered silicate nanocomposites (RPLSNs) were firstly prepared by melt intercalation using sodium montmorillonite (MMT) and ω-amino acid modified MMTs (C3M, C6M, and C12M). Morphology, curing behaviors, mechanical properties, and thermal stabilities of RPLSNs were investigated. Resol type phenolic resin (KL) had hydrophilic methylol groups and low molecular weight species. MMT had a better miscibility with phenolic resin than ω-amino acid modified MMTs at the beginning of cure due to hydrophilicity, but the latter better than the former at the last stage of cure because KL resin changed into hydrophobic. KL resin was rapidly intercalated into silicate at an initial stage of cure but some portions of silicate was stacked by deintercalation of KL resin. RPLSNs with ω-amino acid modified MMT had higher mechanical property than RPLSNs with MMT due to the enhanced interfacial adhesion associated with the end-tethered structure. RPLSNs up to 3wt% of silicate had higher mechanical properties than the neat KL resin. But the mechanical properties of RPLSNs above 4wt% decreased due to the stacked silicates and the steric hindrance effect of silicates on the curing of phenolic resin. RPLSNs showed a slight increase in thermal stability when compared to the neat phenolic resin.