An optoelectronic fiber and methods for forming such a fiber are disclosed. The fiber generally includes an electrically conductive fiber core, a first semiconducting layer substantially surrounding the fiber core, and a second semiconducting layer substantially surrounding the first semiconducting layer. The first and second semiconducting layers are of complementary types, i.e., one is p-type and the other is n-type. The fiber may be made, e.g., by electrospinning a material to form a fiber core; substantially surrounding the fiber with a first semiconducting material; and substantially surrounding the first semiconducting material with a second semiconducting material. Optoelectronic fibers can be fashioned into a web to provide a solar cell material or substantially transparent conductive material.