Novel copper phosphide (Cu3P) hollow spheres have been successfully fabricated in ethylene glycol (EG) by a solvothermal process at low temperature, using newborn copper hydroxide (Cu(OH)(2)) and elemental phosphorus as starting materials. The phase composition and morphology of the products were characterized by means of X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). It is found that reaction temperature, reaction solvents and starting materials play important roles in the formation of the products. It is suggested that the reaction proceeds through a typical solvent-assisted coordination and reduction process, in which EG serves as not only a reducing reagent but also a complexing solvent. The possible mechanism is discussed. (C) 2007 Published by Elsevier B.V.