The influencing factors such as sampling, sample preparation, sample particle size, sample retention time and sample weight in the process of volatile determination of electrode paste were analyzed. The results showed that the sampling and sample preparation of samples could significantly affect the volatile determination results, and the volatile of electrode paste gradually decreased with the retention time of samples. The sample weight has a certain influence on the determination results. The particle size of the sample has little effect on the determination results. Through the precision measurement of the experimental method and the whole process, the results show that the main influence of the detection precision lies in the sampling and sample preparation links.