Valleriite is a typical interstratified mineral with its basic structural sheet in different classes. In its structure, iron ions may occupy two sites: tetrahedral site in sulfide sheet and octahedral site in hydroxide sheet. On the basis of the Mssbauer data obtained at room temperature, the spectral pattern and Mssbauer parameters of valleriite are obtained. The results suggest that high-spin Fe2 is present in tetrahedral site with isomer shift (IS) of 0.42-0. 48 mm/s and quadrupole splitting (QS) of 0.81- 1.28 mm/s, also with a random distribution at this site and lower symmetry of coordination environment;low-spin Fe3 is present in octahedral site with IS of 0.32-0.36 mm/s and QS of 0.44- 0.59 mm/s.