Poly(vinyl alcohol) (PVA)-encapsulated Mn2+-doped ZnS quantum dots (PVA-ZnS:Mn2+ QDs) synthesized at 80 °C in air. The structural property was investigated using X-ray powder diffraction (XRD). The XRD analysis shows that the ZnS:Mn2+ QDs possessed a zinc blende structure and the complexes of ZnS:Mn2+ QDs with PVA molecules have been formed. The photoexcitation energy transfer is found and investigated between PVA molecules and ZnS:Mn2+ QDs using characterization techniques such as Fourier transform infrared spectroscopy (FTIR), UV–vis absorption spectroscopy, photoluminescence excitation (PLE) and photoluminescence (PL) spectroscopy. The studied results show the photoluminescence enhancement of the Mn2+ 4T1(G) – 6A1(S) emission intensity is due to the efficient energy transfer process from the ZnS host lattice and PVA capping molecules to Mn2+ centers. Moreover, Förster resonance energy transfer (FRET) efficiency from PVA molecules to the Mn2+ center within PVA-ZnS:Mn2+ QDs is about 20.28%.