Poly (p-vinylphenol) was derivatized by reaction with ortho- methylolated precursors to introduce ortho-ortho linked phenolic diad and triad moieties onto the polyethylene backbone. In particular, the resulting polymers obtained by the reaction with 2,4-dimethyl-6-methylolphenol were characterized by spectroscopic and lithographic methods to understand the structure/property relationship. The reaction took place in a sequential fashion so that the diad formation was followed by the triad formation. The diad was found to have two conformations, corresponding to hydrogen-bonded and -unbonded states, while the triad existed only in the hydrogen-bonded conformation. The dissolution behavior of the modified polymers with and without DNQ ester was greatly affected by the degree of HMX incorporation. Optimized resist performance determined by dissolution rate monitoring was obtained on modification of all phenolic moieties with a diad/triad ratio of approximately 1.