Over the past years, the high catalytic property of electrospun nanofibers attracted more attention in the field of catalysis. Titanium dioxide (TiO2) electrospun nanofibers and their modifications have become the focus of the photocatalysis research owing to their high surface to volume ratio, high porosity and non-toxicity. So far, however, it has not been applied in the photocatalytic devices because the bad self-supporting is still the main drawback to prevent their practical application. Here, a novel three-dimensional porous membrane of hybrid TiO2/bioglass, which could be adhered on different carriers as "wallpaper" only by a short time of heating, has been fabricated in this work. Though microfluidic electrospinning, the hybrid nanofibrous membrane could be divided into three thin layers according to the components of the fiber. The top layer of the hybrid nanofibrous membrane, containing 90% TiO2 in the fiber, would maintain three-dimensional interconnected porous structure with the increasing of its thickness, revealing highly photocatalytic activity. In addition, the bottom bioglass (70SiO(2)center dot 25CaO center dot 5P(2)O(5)) nanofibrous layer of the hybrid TiO2/bioglass membrane made the membrane adhere on different carriers firmly through heating within 5 s. The hybrid membrane exhibited higher photocatalytic efficiency than the thin film of TiO2, which would be expected to be used in the preparation of photocatalytic devices.