Sorbitol is a primary platform compound in the conversion of cellulose. The conversion of sorbitol to C₆ hydrocarbons requires a complete cleavage of C–O bonds and meanwhile the inhibition of C–C cleavage. Here, we demonstrated an efficient selective cleavage of C–O over C–C bond on the (221) facet of supported CoGa. A selectivity of 94% to C₆ hydrocarbon with conversion of 97% has been achieved. The selective C–O cleavage was demonstrated by tuning the exposed facet as (221) or (110). The supported CoGa was prepared simply by reduction of Co and Ga-containing layered double hydroxides (CoZnGaAl-LDHs), and the exposed facets of CoGa crystallites were controlled by tailoring the temperature-programmed rate in the reduction. By reducing CoZnGaAl-LDHs, CoGa (221) was exposed with a temperature-programmed rate of 5 °C/min under the induction of ZnO lattice, while CoGa (110) was exposed with a rate of 10 °C/min.