TiO2 submicrospheres are used in dye-sensitized solar cells and Li-ion batteries to enhance energy conversion efficiency and volumetric performance. In this study, a microfluidic chip was designed for the realization of the continuous controllable synthesis of TiO2 submicrospheres. The chip utilizes two T-channels to discrete dispersed phases into droplets, and a Y-channel to fuse the two dispersed phase droplets. The droplets generation process, the influencing factors of droplet length and the fusion process of droplets were investigated. The effects of the flow rate ratio of titanium oxysulfate and ammonia solutions, microchannel geometrical profiles including the Y-channel entrance angle on the size of the synthesized TiO2 were studied. The length of the generated droplets was found to decrease with increasing continuous-phase flow rate, and increase with increasing dispersed-phase flow rate and microchannel cross-section area. When the flow rate ratio of titanium oxysulfate solution and ammonia solution was 1:1, the average diameter of TiO2 spheres synthesized was the smallest, around 300 nm. Increasing the microchannel cross-section and Y-channel entrance angle were beneficial in obtaining larger TiO2 submicrospheres. This proposed microfluidic strategy has the potential for applications required continuous synthesis of TiO2 submicrospheres with controllable sizes.