Photoresponsive polymers hold vast potential in the realm of drug delivery. Currently, most photoresponsive polymers use ultraviolet (UV) light as the excitation source. However, the limited penetration ability of UV light within biological tissues serves as a significant hindrance to their practical applications. Given the strong penetration ability of red light in biological tissues, the design and preparation of a novel red-light-responsive polymer with high water stability, incorporating the reversible photoswitching compound and donor-acceptor Stenhouse adducts (DASA) for controlled drug release is demonstrated. In aqueous solutions, this polymer exhibits self-assembly into micellar nanovectors (~33 nm hydrodynamic diameter), facilitating the encapsulation of the hydrophobic model drug Nile red (NR) within the micellar core. Upon irradiation by a 660 nm LED light source, photons are absorbed by DASA, leading to the disruption of the hydrophilic–hydrophobic balance of the nanovector and thereby resulting in the release of NR. This newly designed nanovector incorporates red light as a responsive switch, successfully avoiding the problems of photodamage and limited penetration of UV light within biological tissues, thereby further promoting the practical applications of photoresponsive polymer nanomedicines.