Nanocrystalline materials have been intensely investigated in the recent past due to the novel properties associated with size-quantized particles. We have developed a new method for high yield, solution phase synthesis of nanocrystalline III-V semiconductors which eliminates the use of substituted or unsubstituted Group V hydrides and Group III alkyls. Our approach consists of in situ syntheses of (Na/K)3E (E = P, As, Sb) in aromatic solvents and subsequent reactions of these pnictides with Group III halide solutions in coordinating solvents. The nanocrystalline III-V semiconductors GaP, GaAs, GaSb, InP, InAs and InSb are readily prepared in a wide range of particle sizes (4–36 nm) and in high yields. The resultant Ill-V materials have been characterized by XRD, EDXA, TEM and elemental analyses.