Poly(vinylferrocene) (pVFc) homopolymer was synthesized by free radical polymerization, along with a series of pVFcbased copolymers containing either styrene, vinylanthracene or methylmethacrylate. This report details the electrochemical experiments conducted to examine the stability of the various pVFc based polymers, which is shown to be critically dependent on the extent of copolymerization. A trend was found that when the concentration of co-monomer was decreased, electrochemical stability was enhanced. Furthermore incorporation of a second monomer into the polymer chain produced a profound effect on the scan rate behaviour of the vinylferrocene moiety. As the concentration of co-monomer was decreased, the behaviour tended towards that of a diffusion controlled process. These results are of vital significance for the development of pVFc-based electrochemical sensors.