A new proton-conducting membrane was prepared consisting of uniformly macroporous silica matrix and a proton-conducting gel polymer, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS). Three-dimensionally ordered macroporous silica membrane was fabricated by use of a colloidal template method with mono-dispersed polystyrene beads. Surface sulfonation of the pores in the silica matrix was performed by using 1,3-propanesultone. The sulfonated silica matrix exhibited about 400 times higher proton conductivity than unmodified one. The proton conductivity of the composite membrane was also successfully enhanced by using the sulfonated silica matrix.