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The reduction of silver from an aqueous solution on BiFeO₃ surfaces, activated by visible light, was investigated as a function of crystal and ferroelectric domain orientation. When excited by light with energy between 2.53 and 2.70 eV, BiFeO₃ photochemically reduces silver cations from solution in patterns corresponding to the underlying ferroelectric domain structure. Silver is preferentially reduced on domains with a positive polarization directed toward the surface. The amount of reduced silver depends on whether the component of the domain polarization normal to the surface is positive or negative, but is relatively insensitive to the crystal orientation. It is concluded that the ferroelectric polarization decreases electron drift to the surface in domains with a negative polarization, causing spatially selective photochemical behavior, and that the direction of the polarization is more important than the amplitude.