Copper chalcogenide nanoparticles (NPs) represent a promising material for solar energy conversion, electrical charge storage, and plasmonic devices. However, it is difficult to achieve high-quality NP dispersions in experimentally convenient and technologically preferred aqueous media. Also problematic is the transition from NP dispersion to continuously crystalline nanoscale materials, for instance, nanowires, nanoribbons, or similar high aspect ratio nano/microstructures capable of charge transport necessary for such applications. All previous examples of copper sulfide assemblies contained insulating gaps between NPs. Here we show that aqueous synthesis of high-quality monodispersed high-chalcocite β-Cu2S NPs, with sizes from 2 to 10 nm, is possible. When reaction time increased, the NP shape evolved from nearly spherical particles into disks with predominantly hexagonal shape. Moreover, the monodispersed β-Cu2S NPs were found to spontaneously self-assemble into nanochains and, subsequently, to nanoribbons. The width and length of the nanoribbons were 4-20 nm and 50-950 nm, respectively, depending on the assembly conditions. We observed the formation of the nanoribbons with continuous crystal lattice and charge transport pathways, making possible the utilization of self-assembly processes in the manufacturing of photovoltaic, plasmonic, and charge storage devices.