In this paper, a high-sensitivity microelectromechanical system (MEMS) piezoelectric accelerometer based on a Scandium-doped Aluminum Nitride (ScAlN) thin film is proposed. The primary structure of this accelerometer is a silicon proof mass fixed by four piezoelectric cantilever beams. In order to enhance the sensitivity of the accelerometer, the Sc0.2Al0.8N piezoelectric film is used in the device. The transverse piezoelectric coefficientd31of the Sc0.2Al0.8N piezoelectric film is measured by the cantilever beam method and found to be −4.7661 pC/N, which is approximately two to three times greater than that of a pure AlN film. To further enhance the sensitivity of the accelerometer, the top electrodes are divided into inner and outer electrodes; then, the four piezoelectric cantilever beams can achieve a series connection by these inner and outer electrodes. Subsequently, theoretical and finite element models are established to analyze the effectiveness of the above structure. After fabricating the device, the measurement results demonstrate that the resonant frequency of the device is 7.24 kHz and the operating frequency is 56 Hz to 2360 Hz. At a frequency of 480 Hz, the sensitivity, minimum detectable acceleration, and resolution of the device are 2.448 mV/g, 1 mg, and 1 mg, respectively. The linearity of the accelerometer is good for accelerations less than 2 g. The proposed piezoelectric MEMS accelerometer has demonstrated high sensitivity and linearity, making it suitable for accurately detecting low-frequency vibrations.