Bi(NO3)3 and Na2MoO4 were used as starting materials, amidoxime fiber as carrier to prepare Bi2MoO6/amidoxime fiber (AOCF) via a facile liquid-phase synthesis approach. The structure and composition of the product were determined by powder X-ray diffraction (XRD), scanning electron microscopy(SEM), and energy dispersive spectrometry(EDS). The results showed that the Bi2MoO6 distributed evenly on the surface of the fiber, and combined with the fiber through coordination bond. The results of photodegrading rhodamine B(Rh B) indicated that Bi2MoO6/AOCF had good photocatalytic activity and the catalytic activity was better in acidic condition. Catalyst also revealed good photocatalytic activity on reactive yellow/methylene blue /methyl orange, and after repeated 5 times for Rh B degradation was still up 91.4%. The photocatalytic reaction accorded with first-order kinetics.