In this work, β-NaYF₄:Yb,Er upconversion (UC) film was successfully prepared on silicon (Si) substrate via self-assemble method for the first time. The chemical composition and surface morphology of the UC film were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), water contact angle (WCA), X-ray power diffraction (XRD), and scanning electron microscopy (SEM) measurements. To investigate the effects of KH-560 primer film and chemical reactions on the UC luminescence properties of β-NaYF₄:Yb,Er UC film, decay profiles of the 540 nm and 655 nm radiations were measured. Furthermore, tribological test was applied to qualitatively evaluate the adhesion of the UC film. The results indicate that the UC film has been successfully prepared on Si substrate by covalent chemical bonds. This work provides a facile way to synthesize β-NaYF₄:Yb,Er UC film with robust adhesion to the substrate, which can be applicable for other UC films.