A simple and general method for the preparation of ultrathin, large-area, free-standing films of nanofibrous composite materials was developed. First, positively charged cadmium hydroxide nanostrands of 1.9 nm in diameter and micrometers in length were prepared by mixing dilute aqueous solutions of cadmium chloride and aminoethanol. Negatively charged dye molecules, proteins, nanoparticles, and water-soluble fullerene or carbon nanotubes were mixed with the nanostrands to give a well-dispersed solution of the corresponding nanofibrous composites. After filtration of the dispersions with a polycarbonate membrane filter, uniform films with a thickness of a few tens to hundreds of nanometers and a diameter of a few centimeters were obtained. The films were readily peeled off from the membrane filter by immersion in ethanol. The resultant free-standing films could be further transferred to other substrates, such as quartz plate, gold electrode, and porous alumina membrane, and were characterized by scanning and transmission electron microscopies. We provide herein various nanofibrous free-standing films with optical, biological, metallic, and magnetic properties.