NbSi alloys were prepared by direct electrochemically reducing four mixed Nb2O5 and SiO2 powders (Nb-10Si, Nb-20Si, Nb-30Si, and Nb-37.5Si) in molten CaCl2 electrolyte at 900°C. The samples were characterized with scanning electron microscope (SEM), X-ray diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDX). No oxidized phases were remained by XRD tests. Under SEM, Nb phase was scattered in Nb5Si3 phase for the samples of Nb-10Si, Nb-20Si, and Nb-30Si. For the sample of Nb-37.5Si, only Nb5Si3 was obtained after electrolysis.