Rare earth complex polymer luminescent materials have important practical application value in organic electroluminescence, fluorescence sensing, solar cells and other fields. Herein, we fabricated the luminescent film (recorded as Eu(2mCND)4Na/PMMA@LF) through doped Eu(2mCND)4Na complex with polymethyl methacrylate (PMMA) followed by coating on a PMMA slab. And the antireflective (AR) coatings prepared with acid-catalyzed silica sol (ACSS) and base-catalyzed silica sol (BCSS) were coated on the surface of Eu(2mCND)4Na/PMMA@LF which enhance its transparency increasing from 92% to 98.7%. This is because that the AR coatings have high transmittance and environmental stability. In addition, the luminescent film coated with antireflective coating displays high photo-stability, which was also demonstrated after a 35 h UV LED (∼200 mW/cm2) irradiation. The configuration of luminescent film with anti-reflection performance provides a scalable alternative to the current approaches for creating highly transparent solar windows.