Abstract: At present, geological reference materials are playing very important role in the quality assurance and monitoring system of geological analytical data. The prerequisite to use the reference materials properly is to follow the regulation that the sampling mass must reach the certain mass to make sure the sampling is representative. However, for modern analytical techniques of high sensitivity, the practice sampling mass is only about 20-30mg and is much less than 100 mg which is the minimum sampling mass of geological reference materials widely used. So a great challenge for the minimum sampling mass of geological reference materials has emerged with the development of modern analytical techniques. In this paper, we discuss the problem on the sampling mass of geological analysis as well as the minimum sampling mass of geological reference material and its implication from the view of history evolution and current demand. In addition, the technological measures and steps to solve the problem are presented. At the same time, we try to remind the researchers of analytical methods, quality managers and the developer of reference materials to pay attention to the problem of the sampling mass, so that the analytical techniques quickly developed and the monitoring methods laged behind (including reference materials) could go forward together.