Synthetic routes to polyradicals are briefly reviewed; in addition the synthesis and electrochemical characterization of a novel 2,2,6,6-tetramethylpiperidinyloxy-1-pyrrylacetate(I) (or, TEMPO-1-pyrrylacetate) are reported. Rather than forming a conducting polymer deposit, this monomer coats the electrode with a passivating monolayer, which is electroactive at the nitroxide potential (+0.93 V vs Ag+/0). The cyclic voltammetry of the surface-confined nitroxide not only exhibits typical monolayer behaviour (calculated coverage 0.5 nmol cm-2), but also unusual spikes caused by trapped charge.