The double-exchange (DE) interaction, that is, a ferromagnetic (FM) interaction due to a combination of electron motion and the Hund coupling, is a well-known source of a wide class of FM orders. Here, we show that the DE interaction in highly photoexcited states is antiferromagnetic (AFM). Transient dynamics of quantum electrons coupled with classical spins are analyzed. An ac field applied to a metallic FM state results in an almost perfect Néel state. A time characterizing the FM-to-AFM conversion is scaled by light amplitude and frequency. This hidden AFM interaction is attributable to the electron-spin coupling under nonequilibrium electron distribution.