Group IV nanocrystals, such as, for example, silicon nanocrysals and germanium nanocrystals, with chemically accessible surfaces are produced in solution reactions. Group IV halides can be reduced in organic solvents such as 1,2-dimethoxyethane (glyme), with soluable reducing agents to give halide-terminated group IV nanocrystals, which can then be easily functionalized with alkyl lithium, Grignard or other reagents to synthesize group IV nanocrystals having air and moisture stable surfaces. Synthesis can occur at ambient temperature and pressure.