The nucleation and growth kinetics of highly ordered gold nanocrystal superlattices during the evaporation of nanocrystal colloidal droplets was elucidated by in situ time-resolved small-angle x-ray scattering. We demonstrated for the first time that the evaporation rate can affect the dimensionality of the superlattices. The formation of two-dimensional nanocrystal superlattices at the liquid-air interface of the droplet has exponential growth kinetics that originates from interface crushing.