This study explores the development of a photo-responsive bicomponent electrospun platform and its drug delivery capabilities. This platform is composed of two polymers of poly(lactide-co-glycolide) (PLGA) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). Then, the platform is decorated with plasmonic gold nanostars (Au NSs) that are capable of on-demand drug release. Using Rhodamine-B (RhB) as a model drug, the drug release behavior of the bi-polymer system is compared versus homopolymer fibers. The RhB is incorporated in the PHBV part of the platform, which provides a more sustained drug release, both in the absence and presence of near-infrared (NIR) irradiation. Under NIR exposure, thermal imaging reveals a notable increase in surface temperature, facilitating enhanced drug release. Furthermore, the platform demonstrates on-demand drug release upon multiple NIR irradiation cycles. This platform offers a promising approach for stimuli-responsive drug delivery, making it a strong candidate for on-demand therapy applications.