Thermodynamics for chemical vapor synthesis （CVS） of Nb nanopowder in NbCl5-H2-Ar system was investigated by using FactSage software. The validation experiments were conducted to confirm the thermodynamics points. The results indicate that under the atmospheric pressure, the reduction approach from NbCl5（g） to Nb（s） is a stage-wise process with the formation of complex sub-chlorides, and is controllable at low hydrogen ratio （mole ratio of n（NbCl5）：n（H2）＆lt;1：180） and low temperature （＆lt;1050 ＆#176;C）. Furthermore, a reasonable amount of inert loading gas is favorable to increase the reduction ratio of NbCl5 and the powder yield. The as-synthesized Nb nanopowder with the homogeneous size of 30-50 nm and the powder yield of 85% （mass fraction） is obtained by the CVS process under n（NbCl5）：n（H2）：n（Ar）=1：120：1 and 950 ＆#176;C with the NbCl5 reduction rate of 96.1%.
