A poly(vinylferrocene) (PVFc)/cellulose acetate (CA) fibers were obtained using an electrospinning method. The electrospinning process was controlled in situ with a quartz crystal microbalance (QCM) system. Fiber formation was observed through adjusting PVFc concentration. Morphological characteristics depending on the changes of atomic % ratio value of PVFc/CA electrospun fibers was investigated by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy analysis. Electrochemical behavior of PVFc/CA electrospun fibers was investigated by using cyclic voltammetry measurements based on the Fc(+)/Fc redox couple. The results indicated that PVFc deployed in/on the CA fibers and aggregated arbitrarily on the QCM electrode. The new PVFc/CA electrospun fibers were used for anion sensing.