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Based on the piezoelectric effect, a new type of piezoelectric thrust vector-measuring system for a rocket engine is designed, which is made up of four three-component piezoelectric force sensors, so that 12 output force signals can be generated. Using the theoretical mechanics, the reverse formulas for the thrust vector (namely, the misalignment angle and the offset) are deduced. In order to calibrate the measuring system, a special calibration platform is designed. The calibration results show that the non-linearity and cross talk of the designed piezoelectric thrust vector-measuring system are less than 1 and 5%, respectively. Finally, a practical loading experiment is performed to test the application performance of the thrust vector-measuring system, and the experimental results prove that the thrust vector-measuring system can accurately measure both the magnitude and the direction of the thrust vector.