In this work, we develop a sequential self-assembly approach to fabricate interpenetrated binary supramolecular nanofibers consisting of carbazole oligomer 1-cobalt(II) (1-Co2+) coordination nanofibers and oligomer 2 nanofibers for the sensitive detection of six classes of explosives. When exposed to peroxide explosives (e.g., H2O2), Co2+ in 1-Co2+ coordination nanofibers can be reduced to Co+ that can transfer an electron to the excited 2 nanofibers and thereby quench their fluorescence. On the other hand, when exposed to the other five classes of explosives, the excited 2 nanofibers can transfer an electron to explosives to quench their fluorescence. On the basis of the distinct fluorescence quenching mechanisms, six classes of explosives can be sensitively detected. Herein, we provide a new strategy to design broad-band fluorescence sensors for a rich identification of threats.