A new technique called selective excitation of ions for consecutive activation (SEICA) is proposed for obtaining complementary fragmentation mass spectra from the same precursor ion population. SEICA utilizes precursor ions remaining intact after electron capture dissociation or another ion-electron reaction for efficient MS/MS based on a vibrational excitation (VE) technique, such as infrared multiphoton dissociation. SEICA uses the ability of ion-trapping instruments to detect product ions while retaining inside the trap intact precursor ions, making the latter available for consecutive activation by a VE technique. The possibility of practical implementation of SEICA by software-only modification of a commercial instrument is demonstrated. A 2-fold increase in the efficiency is achieved for both "single-scan" and "multiple-scan" experiments. This improvement can be particularly important for high-sensitivity applications in, for example, proteomics, where limited ECD efficiency poses an obstacle for broad implementation of this technique.