The collection and reuse of roof rainwater can alleviate water shortage for daily life. In this study, polyvinylidene fluoride hollow fiber membranes tuned with three multi-walled carbon nanotubes (pure MWCNTs, MWCNTs-COOH, and MWCNTs-OH) were prepared using a non-solvent induced phase separation method for gravity-driven membrane filtration to purify roof rainwater. The results showed that the MWCNTs were distributed on the membrane surface and throughout the porous structure of the cross-section, which changed the pore structure parameters and hydrophilicity. The pure water flux of the MWCNTs tuned membranes increased by 152.5 % at 1.0 bar, and the rejection rates of humic acid and bovine serum albumin increased from 97.4 % and 75.7 % to 98.9 % and 96.3 %, respectively. The extended Derjaguin, Landau, Verwey, and Overbeek (xDLVO) theory states that the presence of MWCNTs leads to changes in the physicochemical properties of the membrane surface, resulting in membranes with different anti-fouling behaviors. A gravity-driven membrane filtration test was continuously operated for 100 days, and all membranes removed 25.0–26.7 %, 49.5–53.0 %, and 89.0–93.3 % of total dissolved solids, dissolved organic carbon, and turbidity from roof rainwater, respectively. However, the pure MWCNTs modified membrane with relatively hydrophobic properties showed a 12.4 % increase in flux over the unmodified membrane. Importantly, the presence of the MWCNTs in the membrane changed the microbial diversity in the biofilter cake layer.