Functional membranes based on stimuli‐responsive block copolymers have attracted significant attention in the field of membrane separations, which can adjust the pore sizes and the surface properties in response to environmental stimuli. However, it was inconvenient to synthesize stimuli‐responsive block copolymers due to the complexity and inefficiency of the synthesis process. In this work, pH‐ and thermal‐responsive triblock copolymers were synthesized by the one‐pot method to modify PVDF membranes. The modified membranes exhibit good hydrophilicity, and the contact angle of M2 decreased from 74° to 0° within 20 s. Surprisingly, the water flux of the blend membrane is approximately 24 times and 33 times higher than that of the pure membrane, respectively. Besides, the modified membranes also exhibit good pH and thermal response, and superior fouling‐tolerant performance. Overall, these multi‐responsive block copolymers synthesized by a simple one‐pot method have enormous potential for controlled size separation, flux regulation, and many other fields.