Mesoporous silica films with defect-free vertical channels on large length scales have great significance in biomaterials, electrochemical and optical sensors. Herein, mesoporous silica films with vertical orientation on large area (5×5 cm2) substrates were successfully prepared by electrochemical assisted self-assembly (EASA) process. The film permeability, surface macroscopic morphology and mesoporous pore structure were characterized by cyclic voltammetry (CV), scanning electron microscope (SEM), atomic force microscope (AFM), high resolution transmission electron microscope(HRTEM), and 2D grazing incidence small-angle X-ray scattering (2D-GISAXS), respectively. In addition, the optical properties of the films in the extreme ultraviolet region were tested by albedometer. The results show that the obtained film on a large area substrate exhibites good permeability,which suggests that the mesochannels in silica films are vertically oriented, and the mesopore diameter and cell parameters are 2.83 nm and 4.1 nm, respectively. Moreover, the reflectivity reaches up to 75% in the extreme ultraviolet wavelengths (5-11 nm).