Studying nanoscale photophysical processes is mandatory to fully understand the complex optoelectronic properties in semiconductor materials used in photovoltaics and light emitting diodes. In this perspective, we target specific scanning probe techniques, which combine scanning tunneling microscopy (STM) with optical methods to unravel the localized optoelectronic properties of semiconductors under realistic electric and optical fields, down to the nanoscale. Combining optical spectroscopy with STM yields a powerful platform that allows for simultaneous imaging of the surface morphology and the electronic structure down to the atomic level, a resolution that is otherwise not accessible due to the optical diffraction limit. Incident wavelengths spanning the electromagnetic spectrum from the terahertz region to X-rays have been coupled into the STM tip-sample junction to investigate the nanoscale properties of semiconductor materials, whereas the reverse process of luminescence can give insight on local recombination processes. Imagine the potential of a tool capable of detecting both localized absorption and spontaneous and stimulated emission processes of semiconductor materials at the nanoscale. The role of every atom, defect, or electronic interaction could be disentangled, tailored, or harnessed to its maximum capacity.