Phase measuring deflectometry (PMD) is widely used to measure the surface of specular objects. The planar screen used in traditional PMD systems have the drawbacks of a small field of view of measurement and a large virtual image depth range. This problem can be effectively solved by using the curved screen. As the arc structure of the curved screen is different to the planar structure required in Zhang’s method, the existing methods mainly rely on the stereo vision of two cameras to obtain the screen position. This paper presents a novel PMD based on a curved screen and single camera. A method of calibrating a curved screen by constructing a virtual planar screen is presented. The method only needs one camera to calibrate the curved screen directly with high accuracy. In addition, the change from planar screen to curved screen makes the traditional phase-gradient-height relation invalid. Based on the comprehensive analysis of space optical path models, a novel phase-gradient-height relation is presented. The relation is a general formula. It can be used for any curved screen, including the planar screen. Simulation and quantitative comparison experiments verify the accuracy and reliability of the proposed calibration method. The measurement results of concave mirror show that the proposed method has higher accuracy and a larger field of view in measuring specular objects than traditional methods.