Electrospun nanofiber mats are usually applied in fields where their high specific surface area and small pore sizes are important, such as biotechnology or filtration. Optically, they are mostly white due to scattering from the irregularly distributed, thin nanofibers. Nevertheless, their optical properties can be modified and become highly important for different applications, e.g., in sensing devices or solar cells, and sometimes for investigating their electronic or mechanical properties. This review gives an overview of typical optical properties of electrospun nanofiber mats, such as absorption and transmission, fluorescence and phosphorescence, scattering, polarized emission, dyeing and bathochromic shift as well as the correlation with dielectric constants and the extinction coefficient, showing which effects may occur and can be measured by which instruments or used for different applications.