Stimuli-responsive polymers with changeable fluorescent properties have numerous applications in sensing, bioimaging, and detection. Here we describe the facile synthesis of a pH-responsive amphiphilic asymmetric diblock copolymer of acrylic acid and butyl acrylate that incorporates a polarity-sensitive fluorophore. The asymmetric structure enhances the stimuli-responsive behavior: as the environmental pH decreases, the fluorescent intensity of the asymmetric diblock copolymer gradually increases, whereas its symmetric block counterpart shows limited and stepwise change. Besides, this remarkable difference was demonstrated to be concentration-independent, as similar emission behavior was found for both polymers at lower concentrations. These results indicate that the fluorescence properties of the copolymer can be adjusted by rationally designing the copolymer structure. This work provides a novel and general strategy for the design and synthesis of polymeric materials with encapsulated structures showing stimuli-responsive fluorescent properties to be applied as fluorescent probes with a smoothly varying response curve rather than the simple on–off switch that is typical of block copolymer systems.