Graphene/TiO2 nanocrystals hybrid is successfully prepared by directly growing TiO2 nanocrystals on graphene oxide (GO) sheets. The direct growth of nanocrystals on GO sheets was achieved by a two-step method, in which TiO2 was coated on GO sheets by hydrolysis first and crystallized into anatase nanocrystals by hydrothermal treatment in second step. Slow hydrolysis reaction through the use of EtOH/H2O mixed solvents and addition of H2SO4 allows the selectively growing TiO2 on GO and suppressing free growth in solution. The method offers easy access to the GO/TiO2 nanocrystals hybrid with well controlled coating and strong interactions between TiO2 and the underlying GO sheets. The strong coupling could lead to advanced hybrid materials for various applications including photocatalysis. The prepared graphene/TiO2 nanocrystals hybrid has demonstrated superior photocatalytic activity in degradation of rhodamine B over other TiO2 materials, showing an impressive 3-fold photocatalytic enhancement over P25. It is expected that the hybrid material could also be promising for various other applications including lithium ion battery where strong electrical coupling to TiO2 nanoparticles is essential.