Large-scale flooding causes widespread disaster, and harmful pollutant concentration in water following flood affects public safety and the environment. In this study, a numerical model for solving the 2D shallow water equations and the solute transport equation is proposed to simulate overland flood and pollutant transport caused by floods. The present model is verified by comparing the predictions with the analytical solutions and simulation results; sufficiently high computational accuracy is achieved. The model is also used to simulate flood inundation and pollution spread in the area of Hun and Taizi Lane (HTL) in China due to river dike breaches; the results show that the coupling model has excellent performance for simulating the flooding process and the temporal and spatial distribution of pollutants in urban or rural areas. We use remote sensing techniques to acquire the land coverage in the area of HTL based on Landsat TM satellites. The impacts of changed land use on mitigation of flooding waves and pollutant spread are investigated; the results indicate that the land cover changes have an obvious influence on the evolution process of flood waves and pollutant transport in the study areas, where the transport of pollutants is very dynamic during flood inundation in HTL area. Furthermore, the motion of pollutants considering anisotropic diffusion is more reasonable than that due to isotropic dispersion in simulating pollutant transport associated with the flood in urban or farmland environments.