In order to solve the problem of the insufficient range of the traditional fast mirror (FSM) angle measurement system in practical applications, a 2D large-angle FSM photoelectric angle measurement system based on the principle of diffuse reflection is proposed. A mathematical model of the angle measurement system is established by combining the physical properties of the diffuse reflecting plate, such as the rotation angle, rotation center, rotation radius, reflection coefficient and the radius of the diffuse reflecting surface. This paper proposes a method that optimizes the degree of nonlinearity based on this mathematical model. The system is designed and tested. The experimental results show that changing the diffuse reflection surface area can improve the nonlinearity of the angle measurement system effectively. When the radius of the diffuse reflection surface is 3.3 mm, the range is ±20°, the non-linearity is 0.74%, and the resolution can reach up to 2.3″. The system’s body is simple and compact. It is also capable of measuring a wider range of angles while linearity is guaranteed.