This paper presents simulation studies of nanoparticle supercluster (NPSC) nucleation from a temperature quenched system. The nanoparticles are represented as 5 nm, spherical gold nanoparticles ligated with alkane thiols. The pair potential accounts for the van der Waals interaction between the metallic cores and ligand-ligand and ligand-solvent interactions. Phenomena well-known for molecular systems are observed including a prenucleation induction period, fluctuating prenucleation clusters that predominately add monomers one at a time, a critical nucleus size, and growth of NPSCs from solution in the presence of an equilibrium supernatant, all consistent with classical nucleation theory. However, only the largest prenucleating clusters are dense, and the cluster size can occasionally range greater than the critical size in the prenucleation regime until a cluster with low enough energy occurs, then nucleation ensues. Late in the nucleation process, the clusters display a crystalline structure that is a random mix of face-centered cubic (fcc) and hexagonal close-packed (hcp) lattices and indistinguishable from a randomized icosahedra structure.