A new x-ray absorption fine structure (XAFS) method is applied to the air-solution interface. Under the total reflection condition, the XAFS method becomes surface sensitive, enabling the self-assembled monolayer of a metal complex at the solution surface to analyze in situ. Furthermore the introduction of two types of linearly polarized x rays allows us to determine the selective orientation of a planar metal complex at the surface. We obtain spectra for a square planar complex, 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrinato zinc(II) (ZnTPPC) adsorbed on the aqueous solution surface forming a monolayer with two polarized x rays and compared them with spectra of the same compound in a bulk solution and in solid powder. The polarized XAFS spectra exhibit different features leading to the unambiguous conclusion that the plane of the ZnTPPC molecule is oriented parallel to the air-water interface and that there is no coordination to the axial sites of the zinc atom. (C) 2003 American Institute of Physics.