A graphene/TiO2 nanocrystals hybrid has been successfully prepared by directly growing TiO2 nanocrystals on graphene oxide (GO) sheets. The direct growth of the nanocrystals on GO sheets was achieved by a two-step method, in which TiO2 was first coated on GO sheets by hydrolysis and crystallized into anatase nanocrystals by hydrothermal treatment in the second step. Slow hydrolysis induced by the use of EtOH/H2O mixed solvent and addition of H2SO4 facilitates the selective growth of TiO2 on GO and suppresses growth of free TiO2 in solution. The method offers easy access to the GO/TiO2 nanocrystals hybrid with a uniform coating and strong interactions between TiO2 and the underlying GO sheets. The strong coupling gives advanced hybrid materials with various applications including photocatalysis. The prepared graphene/TiO2 nanocrystals hybrid has superior photocatalytic activity to other TiO2 materials in the degradation of rhodamine B, showing an impressive three-fold photocatalytic enhancement over P25. It is expected that the hybrid material could also be promising for various other applications including lithium ion batteries, where strong electrical coupling to TiO2 nanoparticles is essential.