Ni-Na/ diatomite catalysts with different contents of Ni and different binders and pore- expanding agents were prepared by homogeneous precipitation method and equivalent- volume impregnation method, and the catalytic performances were studied. The catalysts were characterized by BET, XRD, NH3-TPD. The addition of Al2O3 greatly enhanced the mechanical strength of catalyst, and the optimum content of Al2O3 was 20%.With the increase of Ni, the dehydrogenation of Ni-Na/ diatomite catalysts increased firstly and then decreased, the catalysts with Ni content of 30% exhibited the best catalytic performance. The adjunction of PEG20000 changed the catalytic construction, increasing the pore size and specific surface area, and improved the selectivity of target product catechol. The research of the fixed bed reaction showed that under the reactions of 320℃ and 101.3kPa, the liquid space velocity was 1.0h-1, conversion of cyclohexanediol and selectivity of catechol for the catalyst Ni/Na diatomite reached 99.4% and 93.%, respectively, and the mechanical strength of catalyst was 85N/cm.