Graphitic carbon/carbon nitride hybrid was fabricated by a two-step procedure from the initially hydrothermal self-assembly of melamine and sucrose and then typical thermal condensation. The structure, composition, photoelectric and photocatalytic properties of the resulting sample was characterized in detail by X-ray diffraction, Fourier transform infrared spectra, Raman spectra, X-ray photoelectron spectroscopy, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, photoelectric current, electrochemical impedance spectroscopy and photocatalytic hydrogen production. The results revealed that the graphitic carbon/carbon nitride hybrid has conjugation effect between carbon nitride and graphitic carbon and thus leads to a better efficiency for water splitting than the pristine carbon nitride.