The paper proposes and verifies a small-angle measurement method based on the defect spot mode of the position-sensitive detector (PSD). With the output characteristics of the PSD in the defect spot mode and the size transformation properties of a focused beam, the measurement sensitivity can be significantly improved. Calibration experiments with the piezoelectric transducer (PZT) indicate that compared with the current PSD-based autocollimation method, the proposed method can improve the sensitivity of small-angle measurement by 57 times, and the measurement sensitivity of the proposed method can be further improved by optimizing the system parameters, while the proposed method has the advantages of a simple system and high real-time performance. Therefore, the proposed method is expected to be used in high-precision motion error detection, as well as in shape and position measurement.