In this paper, we present a room-temperature synthesis of silver dendrites in a poly(vinyl alcohol) (PVA)-Ag composite system with the assistance of high voltage. In the silver dendrites, the nanounits are platelike, thus the surface plasmon absorption bands of silver dendrites are tuned from visible to ~800 nm, which is due to the template function of PVA and the assistance of high voltage. Scanning electron microscope (SEM), X-ray diffraction (XRD), and energy dispersive X-ray (EDX) data confirm that the structures are crystalline silver embedded in PVA. The absorption results indicate that the ratio of PVA and Ag do not influence the position but the intensity of the near-infrared (NIR) absorption. This material has potential use in the field of bio-application and infrared sensors.