Structure of Mo species deposited on a TiO2(110) surface has been studied using in situ polarization-dependent total reflection fluorescence EXAFS (PTRF-EXAFS). We found anisotropic ordering of the Mo species reflecting the anisotropic structure of TiO2 surface when Mo(CO)(6) was deposited under reductive conditions. Mo chains were produced with its Mo-Mo bonding parallel to the [001]direction of the TiO2 substrate. The results provide a possible way to regulate the structure of Mo species on TiO2(110) by the preparation conditions.