We report for the first time the preparation of a fibrous material composed of surface grafted spherical nanosilver and collagen using one-step electrospinning. The resulting composite showed comparable morphology to the control without nanosilver, but had improved electrical conductivity. Under electrical stimulation, fibrous materials containing nanosilver increased connexin-43 expression and proliferation of neonatal cardiomyocytes. Furthermore, composites containing nanosilver prevented biofilm formation but did not activate macrophages.