Wide-band-gap rock-salt (RS) MnS nanocubes were synthesized by the one-pot solvent thermal approach. The edge length of the nanocubes can be easily controlled by prolonging the reaction time (or aging time). We systematically explored the formation of RS-MnS nanocubes and found that the present synthetic method is virtually a combination of oriented aggregation and intraparticle ripening processes. Furthermore, these RS-MnS nanocubes could spontaneously assemble into ordered superlattices via the natural cooling process. The optical and magnetic properties were investigated using measured by UV-vis absorption, photoluminescence spectra, and a magnetometer. The obtained RS-MnS nanocubes exhibit good ultraviolet optical properties depending on the size of the samples. The magnetic measurements suggest that RS-MnS nanocubes consist of an antiferromagnetic core and a ferromagnetic shell below the blocking temperatures. Furthermore, the hysteresis measurements indicate these RS-MnS nanocubes have large coercive fields (e.g., 1265 Oe for 40 nm nanocubes), which is attributed to the size and self-assembly of the samples.