GaN films with highly c-axis preferred orientation are deposited on free-standing thick diamond films by low temperature electron cyclotron resonance plasma enhanced metal organic chemical vapor deposition (ECR-PEMOCVD). The TMGa and N(2) are applied as precursors of Ga and N, respectively. The quality of as-grown GaN films are systematically investigated as a function of deposition temperature by means of X-ray diffraction (XRD) analysis, Hall Effect measurement (HL), room temperature photoluminescence (PL) and atomic force microscopy (AFM). The results show that the dense and uniformed GaN films with highly c-axis preferred orientation are successfully achieved on free-standing diamond substrates under optimized deposition temperature of 400 degrees C, and the room temperature PL spectra of the optimized GaN film show a intense ultraviolet near band edge emission and a weak yellow luminescence. The obtained GaN/diamond structure has great potential for the development of high-power semiconductor devices due to its excellent heat dissipation nature. (C) 2011 Elsevier Ltd. All rights reserved.