In order to achieve high-accuracy measurement of radius of curvature of optical sphere, ultra-high accuracy radius of curvature testing device is developed by dual-frequency laser interferometer and Fizeau interferometer based on cat's eye and confocal method. Through analyzing the error source models of radius of curvature testing, optical configuration of the testing device has been optimized. Precise environment control and real-time monitoring system is also established to reduce the errors caused by environment. Through the above processes, the radius of curvature measurement relative accuracy is better than 2 ppm. One optical sphere, R88.5 mm, test aperture 59 mm, has been tested. Testing result is 88499.465 ± 0.176 μm, meeting the design requirement. The method has high accuracy and practical advantages.