Advancements in wearable technology and lab-on-chip devices necessitate improved integrated microflow pumps with lower driving voltages. This study examines a piezoelectric pump using a flexible β-phase copolymer poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) film. Six samples (S1–S6) were fabricated and subjected to a three-step annealing process to optimize their properties. Characterization was conducted via atomic force microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, impedance analysis, and polarization hysteresis loop measurements. The results show that annealing at approximately 135 degrees Celsius produces a β-phase structure with uniform “rice grain”-like crystallites. A microfluidic pump with a nozzle/diffuser structure, using S4 film as the drive layer, was designed and manufactured. Diaphragm deformation and pump performance were assessed, showing a maximum water flow rate of 25 µL/min at 60 Hz with a peak-to-peak voltage (Vpp) of 60 V. The flow rate could be precisely controlled within 0–25 µL/min by adjusting the Vpp and frequency. This study effectively reduced the driving voltage of the piezoelectric pump, showing that it has significant implications for smart wearable devices.