Shear-induced polymer-bridging flocculation is widely used in the solid–liquid separation process in cemented paste backfill, beneficial to water recycling and tailings management in metal mines. A flocculation kinetics model based on Population Balance Model (PBM) is proposed to model the polymer-bridging flocculation process of total tailings. The PBM leads to a system of ordinary differential equations describing the evolution of the size distribution, and incorporates an aggregation kernel and a breakage kernel. In the aggregation kernel, a collision frequency model describes the particle collision under the combined effects of Brownian motions, shear flow, and differential sedimentation. A semi-empirical collision efficiency model with three fitting parameters is applied. In the breakage kernel, a new breakage rate coefficient model with another three fitting parameters is introduced. Values of the six fitting parameters are determined by minimizing the difference between experimental data obtained from FBRM and modeling result through particle swarm global optimization. All of the six fitting parameters vary with flocculation conditions. The six fitting parameters are regressed with the flocculation factors with six regression models obtained. The validation modeling demonstrates that the proposed PBM quantifies well the dynamic evolution of the floc size during flocculation under the given experimental setup. The investigation will provide significant new insights into the flocculation kinetics of total tailings and lay a foundation for studying the performance of the feedwell of a gravity thickener.