Tetrahedral platinum (Pt) nanocrystals (3-8 nm) are synthesized in high selectivity (ca. 80%) from hydrogen reduction of aqueous K2PtCl6 by using polyvinylpyrrolidone (PVP: Mw≈360000) as a protector. Morphology (TEM) measurements of the metal colloids and UV-Vis absorption of the colloidal solution are employed to monitor the tetrahedron formation during the syntheses with varying K2PtCl6/PVP ratios. The results clearly show a two-stage process for the selective formation of tetrahedral nanocrystals. Rapid nucleation and crystal formation at the early stage result in round-like crystallites and the external facet evolution in thereafter slow crystal growth leads selectively to the formation of the tetrahedrons.