The occurrence of negative magnetoresistance (MR) in semiconductive BaSmFe2O5+w double-perovskite samples is demonstrated. A peak in the MR value was observed at the Verwey–type transition temperature. The transition signifies the charge separation of the Fe2.5+ fluctuating mixed valence state into high-spin Fe2+ and Fe3+. The samples were ferrimagnetic with a Curie temperature of ∼710 K. Upon oxidizing/reducing the samples the size of the MR peak and the temperature at which the peak occurred varied. The largest MR value observed was 1.4% at 7 T.