Porous and single crystalline platinum (Pt) nanoparticles (NPs) have been successfully synthesized by reduction of H₂PtCl₆·6H₂O and then investigated by optical spectroscopy and transmission electron microscopy. H₂PtCl₆·6H₂O was reduced using ethylene glycol in the presence of polyvinylpyrrolidone under highly acidic conditions (pH < 1) to form single crystalline Pt particles about 5 nm in size. These particles were then stacked via {100} facets, forming 50-nm length porous nanocubes with a mosaic structure. The porous Pt NPs exhibited excellent catalytic properties for methanol oxidation. In particular, the electrochemical surface area was ~63 m²/g, five times higher than that for non-porous Pt NPs prepared using a conventional method. We suggest that the high catalytic activity of porous Pt NPs is due to a combination of the crystalline structure having exposed {100} facets and a porous morphology.