Abstract. The principle of detailed balance relates the cross sections σ PR for photorecombination (PR) and σ PI for photoionization (PI) of ions on a state-to-state level. Measuring one or the other of the two cross sections provides direct information about the time-reversed process. Measurements carried out at the Advanced Light Source, Berkeley, for PI of C 2· and Sc 2· are compared with experimental results from the heavy-ion storage ring TSR, Heidelberg, on PR of C 3· and Sc 3· , respectively. From that comparison, state selective cross sections can be inferred both for PR and PI. Both experimental approaches provide possibilities for high-resolution spectroscopy of multiply excited states.