Synthesis of stable and monodisperse Cu nanocrystals of controlled morphology has been a long-standing challenge. In this Article, we report a facile disproportionation reaction approach for the synthesis of such nanocrystals in organic solvents. Either spherical or cubic shapes can be produced, depending on conditions. The typical Cu nanospheres are single crystals with a size of 23.4 ± 1.5 nm, and can self-assemble into three-dimensional (3D) nanocrystal superlattices with a large scale. By manipulating the chemical additives, monodisperse Cu nanocubes with tailorable sizes have also been obtained. The probable formation mechanism of these Cu nanocrystals is discussed. The narrow size distribution results in strong surface plasmon resonance (SPR) peaks even though the resonance is located in the interband transition region. Double SPR peaks are observed in the extinction spectra for the Cu nanocubes with relative large sizes. Theoretical simulation of the extinction spectra indicates that the SPR band located at longer wavelengths is caused by assembly of Cu nanocubes into more complex structures. The synthesis procedure that we report here is expected to foster systematic investigations on the physical properties and self-assembly of Cu nanocrystals with shape and size singularity for their potential applications in photonic and nanoelectronic devices.