NaCa2Si3O8(OH)nanowires with diameters of 100-150 nm and lengths up to several tens of micrometers have been successfully prepared on a large scale via a one-step hydrothermal method. The poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS)-coated NaCa2Si3O8(OH) nanowires have also been prepared via a simple dip-and-dry technique. The electrochemical performances of the NaCa2Si3O8(OH) and NaCa2Si3O8(OH)/PEDOT:PSS nanowires were investigated. Compared with pure NaCa2Si3O8(OH) nanowires, the NaCa2Si3O8(OH)/PEDOT:PSS composite nanowires exhibit improved electrochemical properties of higher discharge/charge capacity and better cycling reversibility. This is the first time that NaCa2Si3O8(OH) nanostructures were used as anode materials in lithium-ion batteries, and the present work will greatly expand the application fields of NaCa2Si3O8(OH).