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Nano-TiO2/poly(methylmethacrylate) nanofibres were prepared by electrospinning with poly(methylmethacrylate) (PMMA) and anatase nano-TiO2 as main materials which were blended mechanically and dissolved in dimethylformamide (DMF) and ethyl ethanoate (EA) solvent. The nanofibres morphologies and physical states were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetry analysis (TG), fourier transform infrared (FTIR) spectroscopy and UV–visible (UV–Vis) spectroscopy. Scanning electron microscopy observations revealed that when the content of TiO2 was 5%, nano-TiO2/poly(methylmethacrylate) nanofibres had the minimum average diameter which was 409 nm. Results from FTIR, XRD and TG suggested that anatase nano-TiO2 had been successfully introduced to the PMMA matrix and TiO2/PMMA nanofibres had good thermal stability within 300 °C. Results from UV–Vis suggested that when 10% of anatase nano-TiO2 was added, the photocatalytic decomposition of methyl orange was 50% higher than that of pure PMMA nanofibres under sunlight irradiation for 5 h. [ABSTRACT FROM AUTHOR]