The　plane-wave　pseudopotential　function　method,　based　on　density-functional　theory,　has　been　used　to　calculate　the　adsorption,　electronic　band　structures,　orbitals　and　optical　absorption　spectrum　of　[Fe(CN)(6)](4-)　on　TiO2　anatase(101)　surface.　Our　calculations　reveal　that　the　surface-modified　anatase　system　has　large　adsorption　energy　and　a　much　narrower　band　gap.　[Fe(CN)(6)](4-)　adsorption　on　the　(101)　surface　could　lead　to　a　large　red　shift　of　the　anatase　optical　absorption　threshold,　which　extends　into　a　visible　region　significantly.　The　calculated　results　are　in　agreement　with　the　experiment　and　other　theoretical　studies　reasonably.　It　is　very　important　for　the　understanding　and　further　development　of　photovoltaic　materials　that　are　active　under　visible　light.