The main analysis error of pressed powder pellet of carbonate comes from particle-size effect and mineral effect. So in the article in order to eliminate the particle-size effect, the ultrafine pressed powder pellet sample preparation is used to the determination of multi-elements and carbon-dioxide in carbonate. To prepare the ultrafine powder the FRITSCH planetary Micro Mill machine and tungsten carbide media is utilized.To conquer the conglomeration during the process of grinding, the wet grinding is preferred. The surface morphology of the pellet is more smooth and neat, the Compton scatter effect is reduced with the decrease in particle size. The intensity of the spectral line is varied with the change of the particle size, generally the intensity of the spectral line is increased with the decrease in the particle size. But when the particle size of more than one component of the material is decreased, the intensity of the spectral line may increase for S, Si, Mg, or decrease for Ca, Al, Ti, K, which depend on the respective mass absorption coefficient . The change of the composition of the phase with milling is also researched. The incident depth of respective element is given from theoretical calculation. When the sample is grounded to the particle size of less than the penetration depth of all the analyte, the effect of the particle size on the intensity of the spectral line is much reduced. In the experiment, when grounded the sample to less than 8μm(d95), the particle-size effect is much eliminated, with the correction method of theoretical αcoefficient and the empirical coefficient , 14 major, minor and trace element in the carbonate can be determined accurately. And the precision of the method is much improved with RSD<2%, except Na2O. Carbon is ultra-light element, the fluorescence yield is low and the interference is serious. With the manual multi-layer crystal PX4, coarse collimator, empirical correction, X-ray spectrometer can be used to determine the carbon dioxide in the carbonate quantitatively. The intensity of the carbon is increase with the times of the measurement and the time delay even the pellet is stored in the dessicator. So employing the latest pressed powder pellet is suggested.