Abstract Herein, we study the preparation and characterization of a new kind of proton exchange membrane. In the proton‐conducting membrane of poly(vinylidene fluoride) (PVDF)/poly(ethylene oxide) (PEO)/dodecyl benzenesulfonic acid (DBS‐H), we use PEO as “proton solvent” due to its flexible molecular chain. Moreover, the electronegativity of the O atom on PEO may be used to attract protons under anhydrous conditions. The membranes are thermally stable up to 200 °C with less than 3 % mass loss. At 150 °C, without extra humidification, the proton conductivity of 60 % PVDF/22 % PEO/18 % DBS‐H membrane is approximately 10 −3 S cm −1 .