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Solvent resistant membrane distillation (SR-MD) is a novel technology to effectively separate water from waste streams containing solvents with high boiling points, avoiding the high chemical costs and release of harmful gas in conventional treatments. Ceramic membranes are promising for this process as they are highly stable chemically but they require modification to tune the hydrophilicity to hydrophobicity. However, the widely used silanization for hydrophobic modification often involves expensive chemicals and may produce toxic substances. Here, we present a new hydrophobic modification method with the use of fatty acid chloride (FAC), as a greener and cheaper alternative to silanes. In the grafting reaction, the acyl chloride groups react with the –OH groups on the ceramic membranes to form strong ester bonds. We successfully grafted stearoyl chloride (SC) and palmitoyl chloride (PC) on the ceramic tubular membranes. With long carbon chains grafted, the modified membranes exhibited high hydrophobicity with a water contact angle >141° and a liquid entry pressure >3 bar. When tested in SR-MD with a feed solution containing 50 wt% dimethyl sulfoxide, the PC-modified membrane demonstrated a flux of 3.2 kg m−2 h−1, with rejection >98% and separation factor >110 at 60 °C, and a high flux of 4.5 kg m−2 h−1 with rejection >96% at 70 °C. The FAC-modified membranes allow a cost-effective treatment of challenging wastewater containing organic solvents through SR-MD. [Display omitted] • Hydrophobic ceramic membranes for solvent resistant MD were synthesized through fatty acid chloride grafting. • The acyl chloride groups formed strong ester bonds on ceramic surface and the modified membranes had high hydrophobicity. • Flux of 3.2 kg m−2 h−1, rejection >98% and separation factor >110 can be achieved when treating 50 wt% DMSO in SR-MD. • The hydrophobicity and separation performance are comparable to ceramic membrane grafted with silanes. • This study presents a greener and cheaper surface modification chemistry to synthesize hydrophobic ceramic membranes. [ABSTRACT FROM AUTHOR]