To develop multifunctional delivery systems of targeted properties for biomedical applications, hybrid fiber-nanoparticle matrices capable of controlled and monitored nanoparticles (NPs) delivery properties were prepared. Firstly, electropinning technique was applied to produce carbon nanotubes (CNTs) incorporated biodegradable poly(ϵ-caprolactone)/gelatin (PG) polymer fibers (PGC fibers). Subsequently, the photoluminescent mesoporous silica nanoparticles (PLMSNs) were electrostatically attached on the surface of PGC fibers to form a localized delivery platform. The PGC-PLMSNs fibers can emit red light under excitation at ~395 nm, 465 nm, and ~533 nm. Additionally, under NIR (808 nm) irradiation, PGC-PLMSNs fibers revealed good photothermal effect. PLMSNs loading efficiency onto the PGC fibers and PLMSNs release kinetics were assessed by TG method. More importantly, the 808 nm NIR irradiation enabled remarkably promoted PLMSNs release rate, validating the typical NIR-triggered release properties. Meanwhile, PLMSNs released from the composite fibers could be optically monitored by decrease in the intensity of red emission. These results suggest the possibility to develop the localized therapeutic device that may inspire other means of treatment method for cancer therapy.