As a bridge between single metal atoms and metal nanoclusters, atomically precise metal complexes are of great significance for controlled synthesis and catalytic applications at the atomic level. Herein, novel Pt2(S-Adam)4(PPh3)2 complexes were prepared via the conventional synthetic methods of metal nanoclusters. The atomically precise crystal structures of the binuclear Pt complexes with three kinds of packing modes in a unit cell were determined by X-ray crystallography. The two Pt atoms are bridged by two S atoms of thiolates, constructing a rhombus on a plane. Moreover, the ultraviolet visible absorption spectra of Pt2(S-Adam)4(PPh3)2 complexes show an apparent absorption peak centered at 454 nm. Furthermore, the Pt complexes were used as precursors to prepare catalysts for non-oxidative propane dehydrogenation. The as-prepared Pt-based catalysts with a particle size of approximately 1 nm demonstrated a propane conversion of about 18% and significantly enhanced selectivity for propylene, up to 93%. Our work will be beneficial to the basic understanding of platinum complexes, as well as the improvement of the catalytic dehydrogenation of propane.