AbstractA novel addition‐cure‐type propargyloligophenol resin for high‐temperature usage was prepared via a two‐step process: Horseradish Peroxidase (HRP) catalyzed oxidation polymerization of phenols to oligophenols, and Williamson etherification of oligophenols to propargyloligophenols. Propargyloligophenols possess an ideal processability for composite manufacture, i.e. good solubility, low melting point (< 50 °C), and thermal curability. As shown by Differential Scanning Calorimetry (DSC), propargyloligophenol resin upon heating experiences a broad thermal exothermic peak in the range of 175–300 °C peaking at around 260 °C. The cured resin is high‐temperature resistant with an initial decomposition temperature > 400 °C and an anaerobic char yield > 60 % at 700 °C. The mechanical properties of glass fabric‐reinforced propargyloligophenol laminate were superior to those of conventional phenolic resins. The results showed that propargyloligophenol resin is a prospective polymeric matrix for high temperature composites.