The rotational speed vectors of the bearing balls affect their service life and running performance. Observing the actual rotational speed of the ball is a prerequisite for revealing its true motion law and conducting sliding behavior simulation analysis. To address the need for accuracy and real-time measurement of spin angular velocity, which is also under high-frequency and high-speed ball motion conditions, a new measurement method of ball rotation vectors based on a binocular vision system is proposed. Firstly, marker points are laid on the balls, and their three-dimensional (3D) coordinates in the camera coordinate system are calculated in real time using the triangulation principle. Secondly, based on the 3D coordinates before and after the movement of the marker point and the trajectory of the ball, the mathematical model of the spin motion of the ball was established. Finally, based on the ball spin motion model, the three-dimensional vision measurement technology was first applied to the measurement of the bearing ball rotation vector through formula derivation, achieving the analysis of bearing ball rolling and sliding characteristics. Experimental results demonstrate that the visual measurement system with the frame rate of 100 FPS (frames per second) yields a measurement error within ±0.2% over a speed range from 5 to 50 RPM (revolutions per minute), and the maximum measurement errors of spin angular velocity and linear velocity are 0.25°/s and 0.028 mm/s, respectively. The experimental results show that this method has good accuracy and stability in measuring the rotation vector of the ball, providing a reference for bearing balls' rotational speed monitoring and the analysis of the sliding behavior of bearing balls.