Electrospun glass nanofibers (EGNFs) were prepared to reinforce polyethylene (PE) plastic waste towards the development of photochromic anti‐counterfeiting patterns and long‐persistent photoluminescent materials, such as smart windows and concrete. By physical integration of lanthanide‐doped aluminate (LdA) nanoparticles (NPs) into polyethylene plastic reinforced with EGNFs, a transparent lanthanide‐doped aluminate nanoparticles (LdANPs)/EGNFs@PE sheet was produced. The colorless EGNFs@PE hybrids became green under ultraviolet (UV) rays and greenish‐yellow in a darkened room as proved by CIE Lab and photoluminescence analysis. In the luminescent LdANPs/EGNFs@PE hybrids, the identified photochromism was promptly reversed at low concentrations of LdANPs to designate fluorescence emission. Photoluminescence was maintained with slow reversibility for the high phosphor concentrations to designate afterglow emission. LdANPs exhibit diameters of 5–12 nm, whereas glass nanofibers have diameters of 70–120 nm. The morphologies of LdANPs/EGNFs@PE substrates were studied by energy‐dispersive x‐ray spectroscopy (EDX), scanning electron microscopy (SEM), and x‐ray fluorescence (XRF). The mechanical properties of the prepared polyethylene plastic were enhanced by reinforcement with glass nanofibers as a roughening agent. The photoluminescent substrates showed markedly improved scratch resistance in comparison to LdANPs‐free EGNFs@PE substrate. The obtained luminescence spectra displayed an emission band at 519 nm upon excitation at 365 nm. The results demonstrated that the luminous plastic has improved hydrophobicity and UV shielding upon increasing the LdANPs content. Glass nanofibers were electrospun to function as reinforcement agent to prepare photochromic, ultraviolet protective, transparent, superhydrophobic, photostable and photoluminescent smart polyethylene plastic sheet.