Surface　organometallic　chemistry　(SOMC)　is　an　effective　route　to　design　and　prepare　surface　metal　species　with　well-defined　composition　and　molecular　structure.　Synchrotron　radiation　X-ray　absorption　fine　structure　spectroscopy　(XAFS)　technique　is　currently　a　powerful　tool　to　characterize　geometrical　structure　of　active　sites　of　solid-state　catalysts.　Their　combination　provided　a　method　to　design　and　construct　in　molecular　level　catalytic　active　centres,　which　was　established　to　be　one　of　the　important　goals　in　the　field　of　heterogeneous　catalysis.　This　article　reviews　the　recent　advancements　in　construction　of　single-site　active　metallic　centre　in　the　channels　and　cages　of　zeolite　molecular　sieves　by　the　SOMC　method　and　in　characterizing　geometrical　structure　of　active　sites　of　heterogeneous　catalytic　materials　with　XAFS,　the　physical　fundament,　experimental　methods,　and　data　analysis　of　XAFS　technique　and　its　merits　and　demerits　in　characterization　of　catalytic　materials,　the　chemical　fundament　of　SOMC.　Single-site　mononuclear　or　polynuclear　Ti,　Cu,　and　Fe　active　centers　were　successfully　constructed　in　molecular　level　in　the　channels　and　cages　of　zeolite　molecular　sieves　by　the　SOMC　method.　Their　micro-structures　were　characterized　in　detail　with　XAFS　combined　other　spectroscopic　techniques　and　their　catalytic　properties　were　evaluated.　The　catalytic　nature　of　these　metallic　centers　was　elucidated　by　establishing　the　inherent　relationship　among　structure,　activity,　and　composition.　The　study　results　revealed　in　molecular　level　the　pyrolysis　mechanism　of　Cu[OCHMeCH　2NM　2]　2　over　the　MCM-41　surface,　and　showed　a　novel　route　to　prepare　CuO,　Cu　2O　and　Cu(0)/MCM-41　materials　with　well-defined　composition　and　micro-structure,　clarifying　the　hydroxylation　mechanism　of　phenol　over　copper　active　sites　and　the　nuclearity-dependent　catalytic　function　of　iron-oxo　species;　based　on　the　binuclear　diiron　[Fe　III-(μ,-0)(μ-OH)-Fe　III]　clusters　with　well-defined　structure　and　composition　constructed　in　molecular　level　by　SOMC,　a　novel　selective　catalytic　reduction　pathway　for　the　iron-catalyzed　NO-HC　reaction　was　proposed;　a　novel　concept　of　＂surface　photoexcited　catalysis　model＂　for　Fe,　Ti　contained　zeolite　molecular　sieve　photocatalysts　and　N-doped　TiO　2　visible-light　photocatalyst　was　proposed　in　terms　of　the　local　structure　of　photoactive　species　identified　clearly　by　XAFS　technique.