Poly(2-methoxy-4-vinylphenol), polyMVP, and poly[(sodium 4-styrenesulfonate)-co-(2-methoxy-4-vinylphenol)] , poly(SSS/MVP), were synthesized by radical polymerization using Vazo-64 or tributylborane as initiator. Poly(3,4-dihydroxystyrene) and poly[(sodium 4-styrenesulfonate)-co-(3,4-dihydro-xystyrene)] were obtained by demethylation of polyMVP and poly(SSS/MVP) using HBr and trimethylsilyl iodide, respectively. (Co)polymer structures were confirmed by H-1 and C-13 NMR spectra. About 30 wt.-% gel formed in the polyMVP polymerizations, whereas only a small amount (0.5 mol-%) of gel formed in the copolymerizations.