This　work　gives　a　first　report　on　the　effective　visible-light-driven　photocatalyst　of　brookite　TiO2(br-TiO2)　hybridized　with　g-C3N4.　This　hybrid　was　prepared　via　a　facile　calcination　in　air.　When　irradiated　under　visible　light,　all　br-TiO2/g-C3N4hybrids　showed　an　activity　superior　to　the　component　g-C3N4or　br-TiO2in　methyl　orange　(MO)　degradation.　The　optimum　photocatalytic　activity　of　the　hybrid　br-TiO2/g-C3N4is　higher　than　those　of　other　types　of　TiO2(anatase　and　rutile)　when　hybridized　with　g-C3N4.　Furthermore,　the　optimized　hybrid,　br-TiO2/g-C3N4(35　wt%),　was　successfully　applied　to　toxic　As3+oxidation　and　water　splitting　for　hydrogen　generation　under　visible　light.　All　these　results　clearly　demonstrate　that　the　hybridization　of　br-TiO2with　g-C3N4is　highly　promising　for　photocatalytic　uses,　which　are　barely　accessible　in　previous　literature.　This　abnormal　observation　is　ascribed　to　the　effective　separation　of　the　photo-generated　carriers　on　the　surfaces　between　the　closely　contacted　br-TiO2and　g-C3N4.　This　journal　is　©　the　Partner　Organisations　2014.