White-light-emitting protocols based on organic materials have received much attention in the academic and industrial fields because of their potential applications in full-color displays and back-lighting units for liquid crystal displays. Here, the attempt is made to fabricate white-light-emitting, electrospun poly(ethylene oxide) (PEO) sheets containing controlled concentrations of a single light-emitting material composed of a type of hyperbranched conjugated polymer (HCP). The HCPs used here have the unique property of exhibiting a variety of fluorescence colors in the electrospun matrix that is caused by the different distances between HCP chains depending on their concentrations, leading to different degrees of intermolecular energy transfer. Therefore, the emission colors of the PEO sheets can be easily manipulated by simply varying the HCP concentrations in the PEO matrix. The resulting method for fabricating nanofibers comprising light-emitting materials in the polymer matrix has great potential for easy fabrication of cost-effective, flexible light-emitting system.