Mesoporous SiO2-P2O5 films were synthesized from the vapor phase onto a silicon substrate. First, a precursor solution of cetyltrimethylammonium bromide (C(16)TAB), H3PO4, ethanol, and water was deposited on a silicon substrate by a spin-coating method. Then, the C(16)TAB-H3PO4 composite film was treated with tetraethoxysilane (TEOS) vapor at 90-180 degrees C for 2.5 h. The H3PO4-C(16)TAB composite formed a hexagonal structure on the silicon substrate before vapor treatment. The TEOS molecules penetrated into the film without a phase transition. The periodic mesostructure of the SiO2-P2O5 films was retained after calcination. The calcined films showed a high proton conductivity of about 0.55 S/cm at room temperature. The molar ratio of P/Si in the SiO2-P2O5 film was as high as 0.43, a level that was not attained by a premixing sol-gel method. The high phosphate group content and the ordered periodic mesostructure contributed to the high proton conductivity.