Hierarchical　porous　TiO　2-carbon　hybrid　composites　with　a　hollow　structure　were　successfully　fabricated　by　a　one-pot　low-temperature　solvothermal　approach　in　the　presence　of　dodecylamine.　The　growth　mechanism　of　the　hierarchical　hollow　spheres　was　demonstrated　to　include　the　condensation　of　a　carbon　source　and　the　co-instantaneous　in　situ　hydrolysis　of　Ti-alkoxide,　and　the　consequent　assembly　of　TiO　2@C　hybrid　nanoparticles　on　a　self-conglobated　template.　As　compared　with　the　TiO　2@C　solid　spheres　(86%),　the　hierarchical　TiO　2@C　hybrid　hollow　spheres　exhibited　an　enhanced　photocatalytic　efficiency　(97%)　for　the　visible-light　photooxidation　of　rhodamine　B.　Investigations　demonstrated　that　the　enhancement　can　be　attributed　to　the　hierarchical　porous　hollow　structure.　Moreover,　the　superoxide　radical　was　detected　as　the　main　active　species　generated　in　the　oxidation　reaction　of　RhB　over　TiO　2@C　photocatalysts.　A　corresponding　mechanism　was　also　proposed　for　the　photocatalysis　process.　©　The　Royal　Society　of　Chemistry　2012.