The invention discloses a method for determining the content of fluorine in a fluorine-containing liquid during the tantalum and niobium hydrometallurgical process, which comprises the steps of preparing a lanthanum nitrate solution, and transferring the lanthanum nitrate solution to a potentiometric titration bottle for calibration; cleaning the pipeline of a potentiometric titrator with pure water, and then moistening the pipeline of the potentiometric titrator with the lanthanum nitrate solution, wherein the titration type is mv titration, the end point parameter is the first end point, theend point jump is middle, and the jump volume is 100.0mv / ml; adding a standard solution of fluorine into a titration cup, adding pure water, placing the solution in the potentiometric titrator for titration, recording the titration volume of lanthanum nitrate, and calculating the titer of lanthanum nitrate according to a formula 1; adding a sample solution into the titration cup, adding ammonia water, pure water and neutral red in sequence, adjusting the sample solution from yellow to red by a hydrochloric acid solution, then placing the solution in the potentiometric titrator for titration,recording the titration volume of lanthanum nitrate, and calculating the content of fluorine in the sample solution according to a formula 2. The method of the invention has the characteristics of high reproducibility, small relative standard deviation in measurement and high accuracy.