Varied metallophthalocyanine intercalated layered double hydroxides (LDHs) as bifunctional hybrid catalysts for selective epoxidation have been prepared and characterized. Systematic characterizations suggested the successful intercalation of the metallophthalocyanines into the interlayer of ZnAl LDHs. The synthesized hybrid exhibited excellent catalytic activity in the selective epoxidation of various olefins through O-2/isobutaldehyde system. The basicity of the hybrid benefits to the selectivity of epoxide, and the bifunctional roles of the catalyst in the reaction have been discussed and verified by a series of controlled experiments. On the basis of obtained results, a probable mechanism of the epoxidation by the hybrid has been proposed and detailedly investigated. Under the catalysis of metallophthalocyanines intercalated LDHs in the presence of O-2/isobutaldehyde, the production of epoxide undergoes two reaction paths. And two types of intermediates, namely acylperoxy radical and peroxyacid, are formed in the reaction, and the former is predominant.