Nanocrystalline particles of copper have been prepared using the solvated metal atom dispersion (SMAD) technique. Their chemical and catalytic reactivity have been tested in the Ullman reaction (aryl homocoupling) and the hydrogenation of CO2 to form CH3OH. The powders obtained from different solvents have surface areas of 24–30 m2/g, particle sizes of 20–45 nm, and crystallite sizes of 8–12 nm. The order of activity found toward the aryl homocoupling reaction is Cu*/toluene > Cu*/THF > Cu*/pentane > Cu*/diglyme, with a maximum biphenyl yield of 90% at 150 °C after 6 h for the Cu*/toluene sample. For the CO2 to CH3OH reaction, a maximum conversion of 80% was obtained for the Cu*/pentane/NC-ZnO sample. In general, the Cu*/nanocrystalline (NC)-ZnO samples show a larger conversion of CO2 to methanol at 450 °C compared with NC-ZnO and NC-ZnO/CuO.