Novel phenolic resins bearing methylol and phenyl ethynyl functions and curing by both condensation and addition mechanisms were synthesized by the reaction of 3-(phenyl ethynyl) phenol (PEP) with formaldehyde under alkaline conditions. Resins with varying relative concentration of the two functional groups were synthesized and characterized. The resins underwent a two-stage cure, confirmed by both DSC and DMA analyses. The low-temperature cure due to methylol condensation led to early gelation of the system. The ultimate curing through addition reaction of phenylethynyl group required heating at 275 degreesC. The cured resins exhibited better thermal stability and anaerobic char yield in comparison to a conventional resole. The thermal stability and char-yielding property showed a diminishing trend with enhanced methylol substitution. Resin with F/P ratio less than unity offered excellent thermal stability and anaerobic char yield. The thermal degradation of the cured resins occurred in two kinetic steps. Methylene groups favored the initial degradation, whereas the higher temperature carbonization process was independent of the network structure.