Mesoporous silica films with vertically aligned hexagonal pores have been produced via the electrochemically assisted surfactant assembly (EASA) method using cetyltrimethylammonium bromide (CTAB) surfactant. Mesoporous silica powder has also been synthesised using the same surfactant. The pore walls of the silica powder and films have been grafted with organosilane reagents. The size of the pore, degree of grafting and effect on the properties of the pore have been investigated using porosimetry, contact angle, NMR and CHN analysis. The degree of grafting was found to be dependent upon the size of the grafting agent, with the smallest steric bulk grafting most effectively. It was found that the grafting of the pores with Me3SiCl greatly increased the hydrophobicity of the pore and reduced water penetration. Grafting with larger groups caused the film surface to be hydrophobic but had little effect on the penetration of water into the pores.