Abstract The pollution of water caused by antibiotics cannot be underestimated. A series of functional nanoparticles and nanofibrous membranes was prepared using oil bath heating method, calcination method, and modified tri–axial electrospinning technology. Various characterizations were used to evaluate the physical and chemical characteristics of functional nanoparticles and nanofibrous membranes. Doxycycline (DC) was chosen as the model pollutant. Functional nanofibrous membrane loaded with β-FeOOH/TiO2 (1/1, w/w) had the best effect on the degradation of DC under natural sunlight, the optimum pH value of degradation was 6, the equilibrium time was 5 h, and the best concentration of H2O2 was 9 mmol/l. Under the optimal pH condition, the highest natural light degradation efficiency of the functional nanofibrous membrane loaded with β-FeOOH/TiO2 (1/1, w/w) to DC was 90.14% within 5 h. The photodegradation process conformed to the Langmuir–Hinshelwood apparent pseudo-first-order kinetic model. Overall, the matched relative energy band potential and good electron-hole conductivity of the two semiconductor materials (β-FeOOH and TiO2) are the key to the enhancement of the DC degradation ability.