Abstract: In this paper we report various factors which affect the voltammetry of PVFc polymer film electrode, and discuss the charge transport process of the polymer film electrode. Size of hydrated anion (counter ion), concentration of the electrolyte, swelling property of the film in the solvent and thickness of the film have significant effects on the voltammetry of the PVFc film electrode. We studied electrocatalysis of Fe(CN)_6~(4-), L-dopa and catechol by PVFc film electrode. We also studied the kinetic processes of these reactants at rotating disk electrode (RDE). The current peaks of the mixture of ascorbic acid and catechol can not be seperated at bare glassy carbon electrode but can be seperated well at PVFc film electrode. This result is meaningful for biochemical analysis.