A powerful method to determine the hidden structural parameters in functional molecules has been developed. Local valence arrangements that dominate the material properties are sometimes not three-dimensionally ordered. This method that comprises diffuse X-ray scattering and resonant X-ray scattering is suitable in such cases. Using this method, we present clear evidence of the low-dimensional valence arrangement in two halogen-bridged one-dimensional metal complexes, so-called MMX chains. This family allows us to control many physical and structural parameters by chemical substitution of bridging halogen, counterions, or metal ions, and one of our samples carries an unusual metallic phase. It is demonstrated with this complex that the present method makes it possible to have microscopic insight to low-dimensionally ordered systems.