New “112” phases, LnBaCo2O5.4, with an ordered oxygen deficient perovskite structure, derived from the YBaFeCuO5-type were studied for Ln=Eu, Gd. The appearance of giant negative magnetoresistance in this structural type is demonstrated. Resistance ratio R0/R7 T reaches at least 10 at 10 K, i.e., is significantly larger than those observed in the other cobalt perovskites, such as La1−xSrxCoO3. These properties are linked to an original magnetic behavior of these materials that exhibit two types of transition—antiferromagnetic to ferromagnetic, and ferromagnetic to paramagnetic—as T increases. This magnetic behavior may be related to a possible I.S. and L.S. spin ordering of trivalent cobalt in pyramidal and octahedral coordinations, respectively. © 1997 American Institute of Physics.