We present a systematic investigation on the roles of some starting reagents commonly used in gold nanoparticle synthesis. Our results show that Au nanoparticles adsorbed with tetraoctylam- monium bromide (TOAB) or TOAB and 1-dodecanethiol (DDT) can self-assemble into spherical aggregates in various hierarchical forms, such as discrete, linear, and two-dimensional arrays, without using any additional structural linkers. Interestingly, aged Au nanoparticles in different interconnected spherical aggregates are highly ordered, showing long-range lattice uniformity. On the basis of our substrate-dependent experiments, it has been revealed that the sphere for- mation, self-assembly, and crystallization of Au nanoparticles in the superlattice take place upon drying. A structural evolution of mesoscale spherical assemblies to planar organizations of Au nanoparticles has also been revealed in this work for the first time. In general, the Au nanopar- ticles are better shelled with TOAB than with DDT surfactant. The symmetrical organic shells of TOAB and its multi-chain structure are believed to be responsible for the high capacity of particle aggregation as well as for the long-range assembling order.