Although there has been considerable research on urban heat island (UHI) effects, most of the previous studies have attributed UHI effects to localized, surface processes. In this study, the impact of upstream urbanization on enhanced UHI effects is examined using surface observations and numerical simulations of an extreme UHI event that occurred on 9 July 2007 over Baltimore, Maryland. Under southwesterly wind, Baltimore experienced higher peak surface temperatures and higher pollution concentrations than did the larger urban area of Washington, D.C. Results from a coupled ultrahigh-resolution mesoscale–urban canopy model with 2001 National Land Cover Data show an advective contribution from upstream urbanization to the UHI event. This dynamical process is demonstrated by replacing Baltimore or its upstream urban areas by natural vegetation (in the model), indicating that the UHI effects could be reduced by as much as 25%. An analysis of the urban–bay interaction reveals the importance of horizontal wind direction in determining the intensity of bay breezes and the urban boundary layer structures. In addition, the vertical growth and structures of UHI effects are shown as layered “hot plumes” in the mixed layer with pronounced rising motions, and these plumes can be advected many kilometers downstream. These findings suggest that judicious land use and urban planning, especially in rapidly developing countries, could help to alleviate UHI consequences, including heat stress and smog. They also have important implications for improving the prediction of urban weather, including the initiation of moist convection, air quality, and other environment-related problems.