The microsphere profile of probe tips has to be measured and compensated to improve the measurement accuracy of micro-coordinate measuring machines (micro-CMMs) to less than several hundred nanometers. A high-precision radius and sphericity measurement method for the microsphere of the CMM probe tip is proposed in this article. Different circumferences of the tested microsphere are measured, and the true radius of any measuring point on the surface can be obtained after separating the runout errors. Then the sphericity of the tested microsphere can be evaluated by the minimum zone sphere (MZS) method. A corresponding measuring system is developed based on the analysis of the primary error model and mechanical model, and verification experiments are conducted using a ruby microsphere (A-5000-7801, Renishaw Corporation) as the reference, whose claimed diameter and sphericity are 700 µm and 130 nm, respectively. Six groups of repeated experiments are performed, and 18000 measurement points on 15 circumferences are recorded in each group of experiments. Results show that the average radius of the tested microsphere is 350.003 µm, and the average sphericity error is 208 nm with a standard deviation of 5.3 nm. Finally, the expanded uncertainty of the measurement results of the developed system is calculated as 209 nm (k=1.96, normal distribution). The proposed method and system can be used in the precision measurements and compensations for probe tips of micro-CMMs and other parts, such as microspheres used in micro-bearings and micro-manufacturing machines.