We have studied the excited states of black phosphorus through the analysis of K and L absorption edges of black phosphorus with energy‐filtered transmission electron microscopy. Energy‐loss spectra exhibit several peaks reflecting features in the density of conduction‐band states at corresponding energies above the vacuum level. We have reproduced the experimental electron energy‐loss near‐edge structures by means of ab initio self‐consistent real‐space multiple‐scattering theory. The comparison of the calculated symmetry‐projected density of unoccupied states and electron energy loss spectra allowed us to assign the spectral features to transitions to specific electronic states.