In recent years, Ti3+ self-doped TiO2 (B-TiO2) exhibits great potential as a photocatalyst. In this work, Ti vapor-assisted annealing is first demonstrated for Ti3+ doping and improving the visible absorption of TiO2. TEM results exhibit the formation of disordered layer, indicating the successful fabricating of B-TiO2. The absorption increase in TiO2 caused by Ti vapor annealing reaches nearly 50% in the visible wavelength range. Benefiting from the absorption increase, the photocatalytic performance of TiO2 after Ti vapor annealing increases by 60-70%. Surface modification of Ag onto B-TiO2 is also carried out to further improve its optical property. Ag-modified Ti3+ self-doped TiO2 (B-TiO2@Ag) exhibits great visible photodegradation behavior to RhB. The RhB degradation rate reaches 97.76% after 60 min of visible light irradiation. Electrochemical performance tests demonstrate that as-prepared TiO2@Ag has lower resistance than W-TiO2. The results indicate that B-TiO2@Ag has great potential in solar photocatalytic degradation of pollutant.