Since the ultrafine reference materials were reported firstly by the “Geoanalysis2003” international conference and the standard SRM2703 for ultrafine marine sediments were published firstly by NIST, the research and development of ultra-fine reference materials and analysis of ultrafine samples had made gratifying progress in China. The research background of ultra-fine reference materials in China was introduced briefly. It was emphasized that the historical evolution of sample size and analytical accuracy promoted alternately in geological analysis and that the analysis of X-ray fluorescence spectrometry had played an important role on finding that sample size had become the key to make further improvement on the analytical accuracy. And the research work on the application of ultra-fine reference materials was reviewed in China, such as carbonate, marine sediments, Platinum group elements in seamount cobalt rich crust, platinum group elements, Gulf estuarine sediments, a variety of minerals. And the research of ultra-fine samples was reviewed by X-ray fluorescence technology and Inductively plasma spectroscopy/mass spectrometry in recent years. The technology and the research work related to the preparation of ultra-fine samples were discussed. The significance of the work and its recent and far-reaching influence on the analytical laboratory were also pointed out.