In this work, sulfur (S) doped (001)-face exposed TiO2 was synthesized via the vapor-thermal method at 180 °C or 250 °C, with an S/Ti molar ratio R
S/Ti of 0, 0.5, 1, 2, 3, 4, and 5. The S-doped samples at 250 °C exhibited significantly improved photocatalytic performance. The effects of S doping were as follows: (1) The S element exhibits different chemical states in the samples with different R
S/Ti. Specifically, it exists in the form of S2− replacing O2− at R
S/Ti = 1, and S6+ replacing Ti4+ at R
S/Ti ≥ 2. As a result, S doping causes a lattice distortion because the ionic radii of S2− and S6+ differ from that of the O2− and Ti4+. (2) S-doping increases the adsorption coefficient A
e
for methylene blue (MB) from 0.9% to 68.5% due to the synergistic effects of the oxygen vacancies, the SO4
2− adsorbed on the TiO2 surface, and the pore size. (3) S-doping increases the MB degradation rate from 6.9 × 10−2 min−1 to 18.2 × 10−2 min−1 due to an increase in the amount of •OH and •O2− radicals.