Nanolaminates are new class of promising nanomaterials with outstanding properties. Here we explored on the tuning of structural properties and the enhancement of electronic and optical properties of 1D PAN ZnO/Al₂O₃ nanolaminates designed by atomic layer deposition (ALD) and electrospinning. The influence of ZnO/Al₂O₃ bilayer thicknesses on the fundamental properties of 1D PAN ZnO/Al₂O₃ nanolaminates has been investigated. Due to the quantum confinement effect, the shift of XPS peaks to higher energies has been observed. Work function of Al₂O₃ was mostly independent of the bilayers number, whereas the ZnO work function decreased with an increase of the bilayer number. Photoluminescence of the 1D PAN ZnO/Al₂O₃ nanolaminates corresponded to emission bands in ZnO nanolayers. Due to quantum confinement and surface band bending, no excitonic peaks were observed. The defect emission band was affected by the band bending and defect concentration. The enhanced photoluminescence of the 1D PAN ZnO/Al₂O₃ nanolaminates allows applications in optical (bio)sensing field