Cubic, rhombic dodecahedral, octahedral, and corner-truncated octahedral gold nanocrystals with sizes of tens of nanometers have been used as building blocks to form micrometer-sized supercrystals by slowly evaporating a water droplet on a substrate placed in a moist environment. Drying the droplet at 90 degrees C was found to yield the best supercrystals. Supercrystals were evenly distributed throughout the entire substrate surface originally covered by the droplet. Diverse supercrystal morphologies have been observed. Nanocubes formed roughly cubic supercrystals. Rhombic dodecahedra were assembled into truncated triangular pyramidal supercrystals. Rhombic dodecahedral, octahedral, and hexapod-shaped supercrystals were generated through the assembly of octahedra. Corner-truncated octahedra formed tetrapod-shaped supercrystals at room temperature, but octahedral, truncated triangular pyramidal, and square pyramidal supercrystals at 90 degrees C. Nanocrystal assembly was found to be strongly shape-guided. Expulsion of excess surfactant to the surfaces of supercrystals suggests that responsive adjustment of surfactant concentration during particle assembly mediates supercrystal formation. Transmission X-ray microscopy and optical microscopy have been employed to follow the supercrystal formation process. Surprising rotational water current near the droplet perimeter carrying the initially formed supercrystals has been observed. Supercrystals appear to grow from the edge of the droplet toward the central region. Supercrystals assembled from octahedra inherently contain void spaces and possibly connected channels. The mesoporosity of these supercrystals was confirmed by infiltrating H2PdCl4 into the supercrystal interior and reducing the precursor to form Pd nanoparticles. The embedded Pd particles can still catalyze a Suzuki coupling reaction, demonstrating the application of these supercrystals for molecular transport, sensing, and catalysis.