A series of TiO2 samples were prepared from the precursor P25 using impregnation method followed by a calcination. The phase compositions of the samples were controlled by addition of various additives, including NaNO3, NaHCO3, Na2SO4, Na3PO4, Na2SiO3, and Na2MoO4. X-ray diffraction patterns demonstrate that the phase transformation from anatase to rutile can be suppressed to a different extent by these additives. Photocatalytic H2 production reactions were performed in methanol aqueous solution. The catalysts, with the addition of NaNO3, NaHCO3, and Na2SO4, show a great improvement in the H2 production activity, while others show a negative effect. This indicates that both the phase structure and the properties of the additives are important for the photocatalytic activity. Infrared spectra of pyridine adsorption on the catalysts reveal that the decreased acidity of the samples may be responsible for the suppressed CO production in the photocatalytic methanol reforming.