Polarized X-ray absorption near-edge structure (XANES) was studied for iodine L(1)-edge an the single crystal of [EDT-TTF(SC18)(2)]I-2(3) which has identical physical properties to the Langmuir-Blodgett (LB) films. The polarization dependence of XANES spectra showed that I-3(-) anions incline 10 degrees from the conducting axis (b axis). Incorporating the present result into the lateral packing model of EDT-TTF(SC18)(2), we proposed a possible molecular arrangement of this system.