The redox conductivity of mixed valent poly(vinylferrocene) films is measured by a steady state method using interdigitated array electrodes. Spectroelectrochemistry shows that the Fc/Fc(+) site concentration ratio has a simple Nernstian dependence on applied potential. Measurements of the bimolecular Fc/Fc(+) electron self-exchange rate constant using concentration gradient- and electrical gradient-driven electron transfers are in agreement and give an average value of 2 x 10(5) M(-1) s(-1) for dry N-2 bathed films. The solid state dispersive transport model of Scher, Montroll, and Pfister is used in interpretation of the electrical potential gradient-driven electron transport. The rate constant k(EX) remains roughly constant as the concentration ratio of Fc(+) and Fc sites is varied from 0.04 to 3.0.