MoS2 hollow microspheres with a high surface activity and superior piezoelectric properties were prepared by a one-step template-free hydrothermal method with MoO3, KSCN and NaF as raw materials. The effects of hydrothermal reaction temperature, reaction time and NaF addition on the preparation of MoS2 hollow microspheres were investigated. The results show that the samples prepared are 1T phase MoS2 hollow microspheres with the sizes of 0.5-1.0 μm at the hydrothermal temperature of 220 ℃, the hydrothermal time of 16 h, and the amount of NaF added of 12 mmol. According to the results of N2 adsorption-desorption experiments, the specific surface area of MoS2 microspheres is 57.67 m2/g, the pore sizes are mainly distributed between 2-6 nm, and the average pore size is 4.25 nm. The catalytic performance of MoS2 microspheres was evaluated via piezoelectric catalytic degradation of methylene blue solution. Under the action of ultrasound, the degradation rate of MB is 89.3%, and Rhodamine B is 98.9% at 60 s. In the degradation of antibiotics in water, the degradation rate of ciprofloxacin within 120 s is 94.7%.