4ZnO center dot B2O3 center dot H2O nano-/microstructures with different morphologies (rod-, wire-, and lamellar-like shapes and microspheres of nano-/microrods) were successfully fabricated through a facile surfactant-assisted hydrothermal method. These 4ZnO center dot B2O3 center dot H2O nano-/microstructures were characterized by XRD, SEM, and BET specific surface area analysis and TEM equipped with SAED. The influence of hydrothermal reaction parameters, including the initial pH, hydrothermal temperature and time, and concentrations of raw materials, on the formation of 4ZnO center dot B2O3 center dot H2O nano-/microstructures was investigated. The surfactant of poly(ethylene glycol) 300 played a crucial role in the formation of crystalline 4ZnO center dot B2O3 center dot H2O-B203-H, 0 with different nano-/microstructures. The structure formation mechanism is briefly discussed. In addition, this work preliminarily demonstrates the fungistatic and bacteriostatic activities of 4ZnO center dot B2O3 center dot H2O nanocrystals.