Electrospinning is a cost-effective and efficient method of producing polymeric nanofibre films. The resulting nanofibres can be produced in a variety of structures, including monoaxial, coaxial (core@shell), and Janus (side-by-side). The resulting fibres can also act as a matrix for various light-harvesting components such as dye molecules, nanoparticles, and quantum dots. The addition of these light-harvesting materials allows for various photo-driven processes to occur within the films. This review discusses the process of electrospinning as well as the effect of spinning parameters on resulting fibres. Building on this, we discuss energy transfer processes that have been explored in nanofibre films, such as Förster resonance energy transfer (FRET), metal-enhanced fluorescence (MEF), and upconversion. A charge transfer process, photoinduced electron transfer (PET), is also discussed. This review highlights various candidate molecules that have been used for photo-responsive processes in electrospun films.