Because structural color is fadeless and dye-free, structurally colored materials have attracted great attention in a wide variety of research fields. In this work, we report the use of a novel structural coloration strategy applied to the fabrication of colorful colloidal fibers. The nanostructured fibers with tunable structural colors were massively produced by colloidal electrospinning. Experimental results and theoretical modeling reveal that the homogeneous and noniridescent structural colors of the electrospun fibers are caused by two phenomena: reflection due to the band gap of photonic structure and Mie scattering of the colloidal spheres. Our unprecedented findings show promise in paving way for the development of revolutionary dye-free technology for the coloration of various fibers.