This paper reports the optical properties of zinc oxide nanofilm fabricated by using organic natural products fromSalvia officinalisleaves (SOL) extract and discusses the effect of the nanocrystal (NC) structure (nanoyarn and nanomat-like structure) on nanofilm optical properties. The surface-active layer of the nanofilm of ZnO nanoparticles (ZnO NPs) was passivated with natural organic SOL leaves hydrothermally, then accumulated on zinc oxide nanorods (ZnO NRs). The nanofilms were fabricated (with and without PEO) on glass substrate (at 85 °C for 16 h) via chemical solution deposition (CSD). The samples were characterized by UV-vis, PL, FESEM, XRD, and TEM measurements. TEM micrographs confirmed the nucleation of ZnO NPs around 4 nm and the size distribution at 1.2 nm of ZnO QDs as an influence of the quantum confinement effect (QCE). The nanofilms fabricated with SOL surfactant (which works as a capping agent for ZnO NPs) represent distinct optoelectronic properties when compared to bulk ZnO. FESEM images of the nanofilms revealed nanoyarn and nanomat-like structures resembling morphologies. The XRD patterns of the samples exhibited the existence of ZnO nanocrystallites (ZnO NCs) with (100), (002), and (101) growth planes. The nanofilms fabricated represented a distinct optical property through absorption and broad emission, as the optical energy band gap reduced as the nanofilms annealed (at120℃). Based on the obtained results, it was established that phytochemicals extracted from organic natural SOL leaves have a distinct influence on zoic oxide nanofilm fabrication, which may be useful for visible light spectrum trapping. The nanofilms can be used in photovoltaic solar cell applications.