Phenolic resin (novolac) has been industrially very important as a curing agent, epoxy resin, adhesive, etc. The materials based on the phenolic resin exhibit a good heat stability, mechanical property, and compatibility with polar polymers. These significant properties are derived from the rigid-rod-like main-chain structure (polyphenylenemethylene backbone) and the reactivities of the phenolic hydroxyl group. We now report functional poly(phenylenemethylene)s as a new class of phenolic resin prepared by the polycondensation of an alkoxybenzene derivative such as anisole and trimethoxybenzene with formaldehyde. The unique polymerization behaviors and properties of the obtained alkoxylated novolacs were observed due to the effect of protecting the phenolic hydroxyl group. Designed phenol (masked phenol derivative) is a versatile tool for design of high-performance phenolic resins and new class of aromatic polymers.