Hydrothermal method has been proven to be an effective method to synthesise the nanostructured titanium dioxide (TiO2) with good morphology and uniform distribution at low temperature. Despite of employing a well-known and commonly used glass substrate as the support to hydrothermally synthesise the nanostructured TiO2, this study emphasised on the application of kaolin hollow fibre membrane as the support for the fabrication of kaolin/TiO2 nanorods (TNR) membrane. By varying the hydrothermal reaction times (2 h, 6 h, and 10 h), the different morphology, distribution, and properties of TiO2 nanorods on kaolin support were observed by field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscope (AFM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). It was found that the well-dispersed of TiO2 nanorods have improved the surface affinity of kaolin/TNR membrane towards water, allowing kaolin/TNR membrane prepared from 10 h of hydrothermal reaction to exhibit the highest water permeation of 165 L/h.m2.bar. In addition, this prepared membrane also showed the highest photocatalytic activity of 80.3% in the decolourisation of reactive black 5 (RB5) under UV irradiation. On top of that, the kaolin/TNR membrane prepared from 10 h of hydrothermal reaction also exhibited a good resistance towards photocorrosion, enabling the reuse of this membrane for three consecutive cycles of photocatalytic degradation of RB5 without showing significant reduction in photocatalytic efficiency towards the decolourisation of RB5.