Supported metal particles are widely used as catalysts in industries but suffer from deactivation because of particle sintering. Here, an efficient and general strategy for the preparation of supported metallic particles with high resistance to sintering is demonstrated by a controllable topological transformation technique of layered double hydroxides (LDHs). This work focuses on the stabilization of CoGa particles developed by our group for catalytic conversion of syngas to alcohols. By the topological transformation of Co and Ga-containing LDHs in a reduction atmosphere, CoGa particles with diverse local structures/environments are produced. The dependence of local structures/environments for CoGa particles on the reduction conditions (temperature, temperature-programmed rate, or holding time) has been revealed. The sintering resistance of CoGa particles has been evaluated by the syngas conversion reaction. The catalytic stability is enhanced with the increase in the Ga-0/Co-0 ratio in CoGa particles and Ga/Co in bulk versus Ga/Co on the surface. Significantly, in addition to a trapped structure, the combination of alloyed Ga-0 species and lattice Ga-III connected to CoGa interfaces primarily contributes to promoting the sintering resistance.