A simple and efficient approach was developed for synthesizing a metal-organic polycatenated compound composed of Ag-triazole complexes and phosphomolybdic acid (PMA) clusters. The hybrid compound, namely {[Ag2(trz)2] [Ag24(trz)18]}[PMo12O40]2 (1) (trz = 1,2,4-triazole), showed high catalytic activity, selectivity and recyclability for the epoxidation of olefins with molecular oxygen as the oxidant and isobutyraldehyde as the co-reagent, and could even work well under ambient conditions. The special polycatenane framework, formed by interlocking [Ag24(trz)18]6+ nanocages, provides suitable space for filling the PMA clusters. The existence of multi-interactions, including π-π stacking, Ag-Ag interactions, and electrostatic interactions, should play a determinative role in fabricating the catalytically active and stable PMA-based polycatenane catalyst for aerobic epoxidation of olefins.