Sulfide persistent luminescent materials are known for their efficient luminescence, although a limitation in application of these materials is their susceptibility to hydrolysis. In this work, the electrospinning technique was used to encapsulate polycrystalline SrS:Eu2+,Sm3+ within PVDF-co-HFP nanofibers, after which thermostimulated luminescence could be observed with the naked eye following treatment with boiling water, confirming that the storage capacity of the powder was maintained after encapsulation. The composite material presented high levels of flexibility, hydrophobicity, and thermal and chemical stability. The structural characteristics of the synthesized SrS:Eu2+,Sm3+ were elucidated using X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The morphologies of the SrS:Eu2+,Sm3+ grains and the electrospun nanofibers were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray fluorescence (XRF) mapping, and scanning transmission X-ray microscopy (STXM). Mechanical properties including elastic modulus and deformation degree were evaluated by PeakForce quantitative nanomechanical mapping (PF-QNM). The luminescent properties were investigated using photoluminescence spectroscopy (PLS), diffuse reflectance spectroscopy (DRS), and X-ray excited optical luminescence (XEOL), which showed that the photonic functionality of the material in the nanofibers was preserved, even after severe treatment with boiling water.