Silver polyhedron coated electrospun nylon 6 nanofibrous membranes were produced using a nonhazardous and “green” electroless process. The process employed sodium citrate as a complexing and reducing agent at 80°C, without the need of any surfactant or hazardous chemicals. The novel nanofibrous membrane, produced under optimum conditions, demonstrated high infrared (IR) extinction and ultraviolet (UV) blocking and good water vapor permeability. It is expected to have wide potential application for thermal radiation shielding, UV blocking and IR camouflage. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011