A new process for one-step extraction of antimony in low temperature from stibnite concentrate by reductive sulfur-fixation smelting in sodium molten salt, using iron oxide as sulfur-fixing agent, was presented. The influences of molten salt addition and composition, ferric oxide dosage, smelting temperature and duration on extraction efficiency of antimony were investigated in details, respectively. The optimum conditions were determined as follows: 1.0 time stoichiometric requirement (α) of mixed sodium salt (αsalt = 1.0), WNaCl:Wsalt = 40%, αFe2O3 = 1.0, Wcoke:Wstibnite = 40%, where W represents weight, smelting at 850 °C (1123 K) for 60 min. Under the optimum conditions, the direct recovery rate of antimony can reach 91.48%, and crude antimony with a purity of 96.00% has been achieved. 95.31% of sulfur is fixed in form of FeS in the presence of iron oxide. Meanwhile, precious metals contained in stibnite concentrate are enriched and recovered comprehensively in crude antimony. In comparison to traditional antimony pyrometallurgical process, the smelting temperature of present process is reduced from 1150–1200 °C (1423–1473 K) to 850–900 °C (1123–1173 K). Sulfur obtained in stibnite is fixed in FeS which avoids SO2 emission owing to the sulfur-fixing agent. Sodium salt can be regenerated and recycled in smelting system when the molten slag is operated to filter solid residue. The solid residue is subjected to mineral dressing operation to obtain iron sulfide concentrate which can be sold directly or roasted to regenerate into iron oxide.