The polymerization behavior of phenolic azosulfonates and triazene by means of enzymatic polymerization using horseradish peroxidase was studied. While for the latter one, only oligomerization was observed, sodium 4‐hydroxybenzenediazosulfonate was successfully homopolymerized. The obtained polymer had an average molecular weight of Mn = 3 000 with a polydispersity index of 1.51. This is the first example of a homopolymer bearing an azosulfonate function in every monomer unit.