In response to the growing demand for high-sensitivity accelerometers in vector hydrophones, a piezoelectric MEMS accelerometer (PMA) was proposed, which has a four-cantilever beam integrated inertial mass unit structure, with the advantages of being lightweight and highly sensitive. A theoretical energy harvesting model was established for the piezoelectric cantilever beam, and the geometric dimensions and structure of the microdevice were optimized to meet the vibration pickup conditions. The sol-gel and annealing technology was employed to prepare high-quality PZT thin films on silicon substrate, and accelerometer microdevices were manufactured by using MEMS technology. Furthermore, the MEMS accelerometer was packaged for testing on a vibration measuring platform. Test results show that the PMA has a resonant frequency of 2300 Hz. In addition, there is a good linear relationship between the input acceleration and the output voltage, with V = 8.412a − 0.212. The PMA not only has high sensitivity, but also has outstanding anti-interference ability. The accelerometer structure was integrated into a vector hydrophone for testing in a calibration system. The results show that the piezoelectric vector hydrophone (PVH) has a sensitivity of –178.99 dB@1000 Hz (0 dB = 1 V/μPa) and a bandwidth of 20~1100 Hz. Meanwhile, it exhibits a good “8” shape directivity and consistency of each channel. These results demonstrate that the piezoelectric MEMS accelerometer has excellent capabilities suitable for use in vector hydrophones.