Silicon, the mainstay semiconductor in microelectronics, is considered unsuitable for optoelectronic applications due to its indirect electronic band gap that limits its efficiency as light emitter. Here, we univocally determine at the nanoscale the origin of visible emission in microstructured black silicon by cathodoluminescence spectroscopy and imaging. We demonstrate the formation of amorphous silicon oxide microstructures with a white emission. The white emission is composed by four features peaking at 1.98 eV, 2.24 eV, 2.77 eV, and 3.05 eV. The origin of such emissions is related to SiOx intrinsic point defects and to the sulfur doping due to the laser processing. Similar results go in the direction of developing optoelectronic devices suitable for silicon-based circuitry.