Water- and airborne environmental threats could be of chemical and biological origin. In global settings, the dangers might stem from toxin chemicals such as VOC and NOx or biological microorganisms such as bacteria, virus, fungi, etc. In this present contribution, the fabrication of broad spectrum photocatalytic multifunctional nanofibers capable of eliminating model chemical and biological toxins was investigated. Co-electrospinning of multicomponent precursors and photoreduction were employed as means to achieve ZnO-TiO2-WO3 hybrid nanofibers and decorate them with nanosilver, respectively. The resulting nanosilver-decorated hybrid nanofibers did not only express their photocatalytic activity, but also unveil resistance against bacteria. The presence of zinc oxide was aimed at effective elimination of fungi and mold. The presence of both tungsten oxide and titanium dioxide, the two chemical elements of visible and UV photocatalytic functions, could lead to cooperative photocatalytic activities under broad spectrum of natural and abundant solar irradiation. Moreover, the superhydrophilicity shown on the nanofibrous layers prepared from these hybrid nanofibers opened the possibility of self-cleaning in broad applications. As a potential application, the hybrid nanofibers might be fabricated into nanofibrous and highly porous membranes which could be advantageous in environmental and hygienic nano-remediation under worldwide natural settings where solar irradiation is highly accessible.