Results of experimental and theoretical investigation of X-ray absorption S K near edge structure in gold complex compounds with isomaleonitrildithiolate and isomaleonitrilthioselenolate ligands are presented. In the framework of a quasi-atomic model the splitting of the 1s^-13p resonance at the sulfur atom has been found to dominate the S K XANES. Approximating the surrounding effect by fragments which include all sulfur and gold atoms a threefold splitting of the resonance was obtained. The components may be attributed to particular σ and π antibonding electronic states of the complex molecule. Comparing the results for both complexes the strong influence of the local structure on the resonance splitting is elucidated.