A facile one-pot synthetic strategy is developed to prepare high-quality Pt supercubes. The as-synthesized Pt supercubes are composed of the uniform Pt nanocubes arranged in a primitive cubic structure. The shape and size of the Pt superparticles are readily tuned by varying the structures of pyridyl-containing ligands used in the synthesis. The co-presence of CO and nitrogen-containing ligands is critical to the formation of Pt supercubes. While CO molecules play an important role in the synthesis of Pt nanocube, introducing nitrogen-containing ligands is essential to the successful assembly of those nanocubes into Pt supercubes. Our systematic studies reveal that the electrostatic attraction between positively charged ligands and negatively charged Pt nanocubes is the main driving force for the assembly of Pt nanocubes into supercubes. More importantly, the ligands within the Pt supercubes are readily removed at relatively low temperature to yield surface-clean supercubes which are expected to exhibit unique size-selective catalysis. The as-synthesized Pt supercubes are composed of the uniform Pt nanocubes arranged in a primitive cubic structure. The shape and size of the Pt superparticles are readily tuned by varying the structures of pyridyl-containing ligands used in the synthesis. The co-presence of CO and nitrogen-containing ligands is critical to the formation of Pt supercubes. While CO molecules play an important role in the synthesis of Pt nanocube, introducing nitrogen-containing ligands is essential to the successful assembly of those nanocubes into Pt supercubes. Our systematic studies reveal that the electrostatic attraction between positively charged ligands and negatively charged Pt nanocubes is the main driving force for the assembly of Pt nanocubes into supercubes. More Importantly, the ligands within the Pt supercubes areiliar removed at relatively low temperature to yield surface-clean supercubes which are e xpected to exhibit unique size-selective catalysis.