Titanium dioxide (TiO2) is the most investigated crystalline oxide in the surface science of metal oxides. Its physical and chemical properties are dominantly determined by its surface condition. Ti3+surface defect (TSD) is one of the most important surface defects in TiO2. According to publications by other groups and the studies carried out in our laboratory, the formation mechanism of TSD is proposed. The generation, properties, and photocatalytic application of TSD are overviewed; the recent exploration of TSD is summarized, analyzed, and evaluated as well in this paper.