The invention discloses a method for determining the content of calcium oxide in raw and auxiliary metallurgical materials. The method comprises the following steps: firstly, according to the sample name of the calcium oxide in the raw and auxiliary materials needing to be determined, selecting a plurality of standard samples of which the variety is the same as that of the sample; secondly, selecting one of the standard samples, and determining the content of the calcium oxide by virtue of a fully-automatic potentiometric titrator, selecting the other standard samples respectively, and determining the content of the calcium oxide in the same way to obtain respective calcium oxide content determination values; thirdly, automatically determining a regression curve equation of a correction value by virtue of linear regression calculation software according to obtained standard calcium oxide content values in the standard samples and the respective calcium oxide content determination values; finally, operating a to-be-determined sample according to the steps, inputting various obtained data into the regression curve equation of the correction value, so that a content correction value of the calcium oxide in a to-be-determined calcium-containing sample can be obtained by calculation. The practice proves that the method is easy to operate and a determination result is high in accuracy.