The invention discloses a composite sodium salt for producing sodium stannate from cassiterite concentrate and an application of the composite sodium salt. The composite sodium salt consists of 70%-90% of sodium carbonate, 5%-20% of sodium bicarbonate, 2.5%-5% of sodium borate and 2.5%-5% of sodium humate by mass. When the composite sodium salt is used, the composite sodium salt is ground to the particles with the size fraction of minus 0.1mm being no less than 90% by mass, the cassiterite concentrate of the fine fraction and the composite sodium salt are mixed according to the mass ratio of 1:(0.5-2), pelletized and dried, coke powder or anthracite is taken as a reducing agent, the mixture is calcined for 30 minutes-90minutes at the temperature of 800 DEG C-950 DEG C, and the cooled calcined product is ground, leached, filtered, purified, concentrated and crystallized, so that the sodium stannate product is obtained. The adopted composite sodium salt is reasonable in component, can be widely obtained, is low in price, is easy to obtain and does not cause pollution to the environment. With the composite sodium salt, the stable crystal structure of the cassiterite concentrate can be obviously damaged, and the composite sodium salt can be widely applied to various cassiterite concentrates so as to directly produce sodium stannate.